Reaction of carbon black with diazonium salts, resultant carbon black products and their uses

ABSTRACT

Processes for preparing a carbon black product having an organic group attached to the carbon black. In one process at least one diazonium salt reacts with a carbon black in the absence of an externally applied electric current sufficient to reduce the diazonium salt. In another process at least one diazonium salt reacts with a carbon black in a protic reaction medium. Carbon black products which may be prepared according to process of the invention are described as well as uses of such carbon black products in plastic compositions, rubber compositions, paper compositions, and textile compositions.

This application is a continuation-in-part of U.S. patent applicationSer. No. 08/356,660, filed Dec. 15, 1994, abandoned the disclosure ofwhich is herein incorporated by reference.

FIELD OF THE INVENTION

This invention relates to a process for the preparation of carbon blackproducts. The process involves reacting a diazonium salt with a carbonblack to yield a carbon black product having an organic group attachedto the carbon black. The invention also relates to new carbon blackproducts and their uses.

BACKGROUND OF THE INVENTION

Much effort has been expended over the last several decades to modifythe surface chemistry of carbon black. While it is possible to depositphysically adsorbed material onto the surface of carbon black,permanently changing the surface chemistry of carbon black issubstantially more difficult.

Some processes for chemically changing the surface of carbon black areknown and used commercially. For example, it is well known that a carbonblack surface can be oxidized with a variety of treating agents. Surfaceoxidation is used to make some commercial products. Sulfonation usingsulfuric acid or chlorosulfuric acid and halogenation of a carbon blacksurface are also known. Some known methods for grafting polymers to thecarbon black surface are reviewed by Tsubakowa in Polym. Sci., Vol. 17,pp 417-470, 1992. See also U.S. Pat. No. 4,014,844 which grafts polymersonto carbon black by contacting the carbon black with the polymer andheating.

U.S. Pat. No. 3,479,300 describes carbon catalyst compositions and aprocess for their production. The catalyst compositions are prepared bytreating carbon particles with an alkali or alkaline earth metal andsubsequently treating the resulting carbon/metal composition with asolvating ether. The carbon portions of the catalytic compositions canbe reacted with various reagents, including organic compounds, toproduce carbon compositions.

U.S. Pat. No. 3,043,708 describes modified carbon blacks havinghydrocarbon groups chemically attached to the surface of the carbonblack. The modified carbon blacks are prepared by reacting carbon blackwith an alkylating agent in the presence of a Friedel-Crafts typereaction catalyst. The hydrocarbon groups which reportedly can attach tothe surface of the carbon black include aliphatic and aromatic groups. Amodified carbon black containing aryl groups attached to the surface ofa carbon black is reported as being preparable by reacting a halogenatedcarbon black with an aromatic hydrocarbon in the presence of aFriedel-Crafts type catalyst. U.S. Pat. No. 3,025,259 describes rubbercompositions containing the modified carbon blacks of U.S. Pat. No.3,043,708.

U.S. Pat. No. 3,335,020 describes modified carbon blacks where thecarbon black is treated with benzene which is then polymerized on thecarbon black. To prepare these modified carbon blacks, benzene andcarbon black are mixed with a Lewis Acid catalyst under anhydrousconditions for about ten minutes. The benzene on the carbon black isthen polymerized to parapolyphenyl by means of a combinationco-catalyst-oxidizing agent and is reportedly thereby bonded to thecarbon black.

U.S. Pat. Nos. 2,502,254 and 2,514,236 describe the manufacture ofpigments containing carbon black. U.S. Pat. No. 2,502,254 reports thathighly dispersed pigments suitable for mass pigmentation of viscose canbe obtained by generating an azo pigment in the presence of carbonblack.

The pigment is produced by coupling a diazotized amine and another usualintermediate for a yellow, orange, or red pigment in the presence ofcarbon black in one or the other of the aqueous solutions of which themixing brings about the coupling. U.S. Pat. No. 2,514,236 reports thatthis process can also prepare a chocolate brown pigment by coupling onemolecular proportion of a tetrazotized benzidine with two molecularproportions of an arylmethyl pyrazolone in the presence of carbon black.

PCT Patent Application No. WO 92/13983 describes a process for modifyingthe surfaces of carbon-containing materials by electrochemical reductionof diazonium salts. The process is reportedly applicable, in particular,to carbon plates and carbon fibers for composite materials.Carbon-containing materials modified by the process are also described.Electrochemical reduction of diazonium salts containing functionalizedaryl radicals to covalently modify carbon surfaces is also described inDelmar et al., J. Am. Chem. Soc. 1992, 114, 5883-5884.

According to WO 92/13983, the process for modifying the surface of acarbon-containing material consists of grafting an aromatic group to thesurface of this material by electrochemical reduction of a diazoniumsalt including this aromatic group. The carbon-containing material isplaced in contact with a diazonium salt solution in an aprotic solventand is negatively charged with respect to an anode which is also incontact with the diazonium salt solution. Use of a protic solvent isreported to prevent the electrochemical process from producing theintended product as a result of reducing the diazonium triple bond toyield a hydrazine.

Despite the technology discussed above, there remains a need to modifythe surface chemistry of carbon black and impart desired properties tothe carbon black.

SUMMARY OF THE INVENTION

Accordingly, the present invention relates to processes for preparing acarbon black product having an organic group attached to the carbonblack. One process comprises the step of reacting at least one diazoniumsalt with a carbon black in the absence of an externally appliedelectric current sufficient to reduce the diazonium salt. Anotherprocess comprises the step of reacting at least one diazonium salt witha carbon black in a protic reaction medium.

Other embodiments of the invention relate to novel carbon blackproducts, which may be prepared according to a process of the invention.The carbon black products may be used in the same applications asconventional carbon blacks. Such uses include, but are not limited to,plastic compositions, aqueous inks, aqueous coatings, rubbercompositions, paper compositions, and textile compositions.

The description which follows sets out additional features andadvantages of the invention. These functions will be apparent from thatdescription or may be learned by practice of the invention as described.The objectives and other advantages will be realized and attained by theprocesses, products, and compositions particularly pointed out in thedescription below and the appended claims.

DETAILED DESCRIPTION Processes for Preparing a Carbon Black Product

A first embodiment of the invention provides processes for preparing acarbon black product having an organic group attached to the carbonblack. One process involves the reaction of at least one diazonium saltwith a carbon black in the absence of an externally applied currentsufficient to reduce the diazonium salt. That is, the reaction betweenthe diazonium salt and the carbon black proceeds without an externalsource of electrons sufficient to reduce the diazonium salt. Mixtures ofdifferent diazonium salts may be used in the process of the invention.This process can be carried out under a variety of reaction conditionsand in any type of reaction medium, including both protic and aproticsolvent systems or slurries.

In another process, at least one diazonium salt reacts with a carbonblack in a protic reaction medium. Mixtures of different diazonium saltsmay be used in this process of the invention. This process can also becarried out under a variety of reaction conditions.

Preferably, in both processes, the diazonium salt is formed in situ. Ifdesired, in either process, the carbon black product can be isolated anddried by means known in the art. Furthermore, the resultant carbon blackproduct can be treated to remove impurities by known techniques. Thevarious preferred embodiments of these processes are discussed below andare shown in the examples.

Any carbon black may be used in the processes of this invention. Theresulting carbon black products are useful in applications known forconventional carbon blacks. The properties of the carbon blacks areselected based upon the intended application. More importantly, theprocesses of this invention can be used to provide carbon black productshaving advantageous properties not associated with conventional carbonblacks.

The processes of the invention can be carried out under a wide varietyof conditions and in general are not limited by any particularcondition. The reaction conditions must be such that the particulardiazonium salt is sufficiently stable to allow it to react with thecarbon black. Thus, the processes can be carried out under reactionconditions where the diazonium salt is short lived. As the examplesbelow illustrate, the reaction between the diazonium salt and the carbonblack occurs, for example, over a wide range of pH and temperature. Theprocesses can be carried out at acidic, neutral, and basic pH.Preferably, the pH ranges from about 1 to 9. The reaction temperaturemay preferably range from 0° C. to 100° C.

Diazonium salts, as known in the art, may be formed for example by thereaction of primary amines with aqueous solutions of nitrous acid. Ageneral discussion of diazonium salts and methods for their preparationis found in Morrison and Boyd, Organic Chemistry, 5th Ed., pp. 973-983,(Allyn and Bacon, Inc. 1987) and March, Advanced Organic Chemistry:Reactions, Mechanisms, and Structures, 4th Ed., (Wiley, 1992). Accordingto this invention, a diazonium salt is an organic compound having one ormore diazonium groups.

In the processes of the invention, the diazonium salt may be preparedprior to reaction with the carbon black or, more preferably, generatedin situ using techniques known in the art. In situ generation alsoallows the use of unstable diazonium salts such as alkyl diazonium saltsand avoids unnecessary handling or manipulation of the diazonium salt.In particularly preferred processes of this invention, both the nitrousacid and the diazonium salt are generated in situ. Each of thesevariations is shown in the examples below.

A diazonium salt, as is known in the art, may be generated by reacting aprimary amine, a nitrite and an acid. The nitrite may be any metalnitrite, preferably lithium nitrite, sodium nitrite, potassium nitrite,or zinc nitrite, or any organic nitrite such as for exampleisoamylnitrite or ethylnitrite. The acid may be any acid, inorganic ororganic, which is effective in the generation of the diazonium salt.Preferred acids include nitric acid, HNO₃, hydrochloric acid, HCl, andsulfuric acid, H₂ SO₄.

The diazonium salt may also be generated by reacting the primary aminewith an aqueous solution of nitrogen dioxide. The aqueous solution ofnitrogen dioxide, NO₂ /H₂ O, provides the nitrous acid needed togenerate the diazonium salt.

Generating the diazonium salt in the presence of excess HCl may be lesspreferred than other alternatives because HCl is corrosive to stainlesssteel. Generation of the diazonium salt with NO₂ /H₂ O has theadditional advantage of being less corrosive to stainless steel or othermetals commonly used for reaction vessels. Generation using H₂ SO₄/NaNO₂ or HNO₃ /NaNO₂ are also relatively non-corrosive.

In general, generating a diazonium salt from a primary amine, a nitrite,and an acid requires two equivalents of acid based on the amount ofamine used. In an in situ process, the diazonium salt can be generatedusing one equivalent of the acid. When the primary amine contains astrong acid group, adding a separate acid may not be necessary in theprocesses of the invention. The acid group or groups of the primaryamine can supply one or both of the needed equivalents of acid. When theprimary amine contains a strong acid group, preferably either noadditional acid or up to one equivalent of additional acid is added to aprocess of the invention to generate the diazonium salt in situ. Aslight excess of additional acid may be used. One example of such aprimary amine is para-aminobenzenesulfonic acid (sulfanilic acid).Others are shown in the examples below.

In general, diazonium salts are thermally unstable. They are typicallyprepared in solution at low temperatures, such as 0°-5° C., and usedwithout isolation of the salt. Heating solutions of some diazonium saltsmay liberate nitrogen and form either the corresponding alcohols inacidic media or the organic free radicals in basic media.

However, to accomplish the process of the invention, the diazonium saltneed only be sufficiently stable to allow reaction with the carbonblack. Thus, the processes of the present invention can be carried outwith some diazonium salts otherwise considered to be unstable andsubject to decomposition. Some decomposition processes may compete withthe reaction between the carbon black and the diazonium salt and mayreduce the total number of organic groups attached to the carbon black.Further, the reaction may be carried out at elevated temperatures wheremany diazonium salts may be susceptible to decomposition. Elevatedtemperatures may also advantageously increase the solubility of thediazonium salt in the reaction medium and improve its handling duringthe process. However, elevated temperatures may result in some loss ofthe diazonium salt due to other decomposition processes.

The processes of the invention can be accomplished by adding thereagents to form the diazonium salt in situ, to a suspension of carbonblack in the reaction medium, for example, water. Thus, a carbon blacksuspension to be used may already contain one or more reagents togenerate the diazonium salt and the process of the inventionaccomplished by adding the remaining reagents. Some permutations of suchprocesses are shown in the examples below.

Reactions to form a diazonium salt are compatible with a large varietyof functional groups commonly found on organic compounds. Thus, only theavailability of a diazonium salt for reaction with a carbon black limitsthe processes of the invention.

The processes of this invention can be carried out in any reactionmedium which allows the reaction between the diazonium salt and thecarbon black to proceed. Preferably, the reaction medium is asolvent-based system. The solvent may be a protic solvent, an aproticsolvent, or a mixture of solvents. Protic solvents are solvents, likewater or methanol, containing a hydrogen attached to an oxygen ornitrogen and thus are sufficiently acidic to form hydrogen bonds.Aprotic solvents are solvents which do not contain an acidic hydrogen asdefined above. Aprotic solvents include, for example, solvents such ashexanes, tetrahydrofuran (THF), acetonitrile, and benzonitrile. For adiscussion of protic and aprotic solvents see Morrison and Boyd, OrganicChemistry, 5th Ed., pp. 228-231, (Allyn and Bacon, Inc. 1987).

The processes of this invention are preferably carried out in a proticreaction medium, that is, in a protic solvent alone or a mixture ofsolvents which contains at least one protic solvent. Preferred proticmedia include, but are not limited to water, aqueous media containingwater and other solvents, alcohols, and any media containing an alcohol,or mixtures of such media.

According to the processes of the invention, the reaction between adiazonium salt and a carbon black can take place with any type of carbonblack, for example, in fluffy or pelleted form. In one embodimentdesigned to reduce production costs, the reaction occurs during aprocess for forming carbon black pellets. For example, a carbon blackproduct of the invention can be prepared in a dry drum by spraying asolution or slurry of a diazonium salt onto a carbon black.Alternatively, the carbon black product can be prepared by pelletizing acarbon black in the presence of a solvent system, such as water,containing the diazonium salt or the reagents to generate the diazoniumsalt in situ. Aqueous solvent systems are preferred. Accordingly,another embodiment of the invention provides a process for forming apelletized carbon black comprising the steps of: introducing a carbonblack and an aqueous slurry or solution of a diazonium salt into apelletizer, reacting the diazonium salt with the carbon black to attachan organic group to the carbon black, and pelletizing the resultingcarbon black having an attached organic group. The pelletized carbonblack product may then be dried using conventional techniques.

In general, the processes of the invention produce inorganicby-products, such as salts. In some end uses, such as those discussedbelow, these by-products may be undesirable. Several possible ways toproduce a carbon black product according to a process of the inventionwithout unwanted inorganic by-products or salts are as follows:

First, the diazonium salt can be purified before use by removing theunwanted inorganic by-product using means known in the art. Second, thediazonium salt can be generated with the use of an organic nitrite asthe diazotization agent yielding the corresponding alcohol rather thanan inorganic salt. Third, when the diazonium salt is generated from anamine having an acid group and aqueous NO₂, no inorganic salts areformed. Other ways may be known to those of skill in the art.

In addition to the inorganic by-products, a process of the invention mayalso produce organic by-products. They can be removed, for example, byextraction with organic solvents. Other ways may be known to those ofskill in the art.

Carbon Black Products

The reaction between a diazonium salt and a carbon black according to aprocess of this invention forms a carbon black product having an organicgroup attached to the carbon black. The diazonium salt may contain theorganic group to be attached to the carbon black. Thus, the presentinvention relates to carbon black products having an organic groupattached to the carbon black, particularly those prepared by a processof this invention. It may be possible to produce the carbon blackproducts of this invention by other means known to those skilled in theart.

The organic group may be an aliphatic group, a cyclic organic group, oran organic compound having an aliphatic portion and a cyclic portion. Asdiscussed above, the diazonium salt employed in the processes of theinvention can be derived from a primary amine having one of these groupsand being capable of forming, even transiently, a diazonium salt. Theorganic group may be substituted or unsubstituted, branched orunbranched. Aliphatic groups include, for example, groups derived fromalkanes, alkenes, alcohols, ethers, aldehydes, ketones, carboxylicacids, and carbohydrates. Cyclic organic groups include, but are notlimited to, alicyclic hydrocarbon groups (for example, cycloalkyls,cycloalkenyls), heterocyclic hydrocarbon groups (for example,pyrrolidinyl, pyrrolinyl, piperidinyl, morpholinyl, and the like), arylgroups (for example, phenyl, naphthyl, anthracenyl, and the like), andheteroaryl groups (imidazolyl, pyrazolyl, pyridinyl, thienyl, thiazolyl,furyl, indolyl, and the like). As the steric hinderance of a substitutedorganic group increases, the number of organic groups attached to thecarbon black from the reaction between the diazonium salt and the carbonblack may be diminished.

When the organic group is substituted, it may contain any functionalgroup compatible with the formation of a diazonium salt. Preferredfunctional groups include, but are not limited to, R, OR, COR, COOR,OCOR, carboxylate salts such as COOLi, COONa, COOK, COO⁻ NR₄ ⁺, halogen,CN, NR₂, SO₃ H, sulfonate salts such as SO₃ Li, SO₃ Na, SO₃ K, SO₃ ⁻ NR₄⁺, OSO₃ H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂, PO₃ H₂, phosphonate saltssuch as PO₃ HNa and PO₃ Na₂, phosphate salts such as OPO₃ HNa and OPO₃Na₂, N═NR, NR₃ ⁺ X⁻, PR₃ ⁺ X⁻, S_(k) R, SSO₃ H, SSO₃ ⁻ salts, SO₂ NRR',SO₂ SR, SNRR', SNQ, SO₂ NQ, CO₂ NQ, S-(1,4-piperazinediyl)-SR,2-(1,3-dithianyl) 2-(1,3-dithiolanyl), SOR, and SO₂ R. R and R', whichcan be the same or different, are independently hydrogen, branched orunbranched C₁ -C₂₀ substituted or unsubstituted, saturated orunsaturated hydrocarbon, e.g., alkyl, alkenyl, alkynyl, substituted orunsubstituted aryl, substituted or unsubstituted heteroaryl, substitutedor unsubstituted alkylaryl, or substituted or unsubstituted arylalkyl.The integer k ranges from 1-8 and preferably from 2-4. The anion X⁻ is ahalide or an anion derived from a mineral or organic acid. Q is(CH₂)_(w), (CH₂)_(x) O(CH₂)_(z), (CH₂)_(x) NR(CH₂)_(z), or (CH₂)_(x)S(CH₂)_(z), where w is an integer from 2 to 6 and x and z are integersfrom 1 to 6.

The carbon black product can comprise a carbon black and at least oneorganic group having a) an aromatic group and b) a cationic group,wherein at least one aromatic group of the organic group is attached tothe carbon black. The organic group can be, for example, X⁻ R₃ N⁺ CH₂COAr, wherein R is a substituted or unsubstituted C₁ -C₁₀ aikyl, Ar isphenylene or naphthylene, and X⁻ is a halide or an anion derived from amineral or organic acid.

A preferred organic group is an aromatic group of the formula A_(y)Ar--, which corresponds to a primary amine of the formula A_(y) ArNH₂.In this formula, the variables have the following meanings: Ar is anaromatic radical such as an aryl or heteroaryl group. Preferably, Ar isselected from the group consisting of phenyl, naphthyl, anthracenyl,phenanthrenyl, biphenyl, pyridinyl, benzothiadiazolyl, andbenzothiazolyl; A is a substituent on the aromatic radical independentlyselected from a preferred functional group described above or A is alinear, branched or cyclic hydrocarbon radical (preferably containing 1to 20 carbon atoms), unsubstituted or substituted with one or more ofthose functional groups; and y is an integer from 1 to the total numberof --CH radicals in the aromatic radical. For instance, y is an integerfrom 1 to 5 when Ar is phenyl, 1 to 7 when Ar is naphthyl, 1 to 9 whenAr is anthracenyl, phenanthrenyl, or biphenyl, or 1 to 4 when Ar ispyridinyl.

In the above formula, specific examples of R and R' are NH₂ --C₆ H₄ --,CH₂ CH₂ --C₆ H₄ --NH₂, CH₂ --C₆ H₄ --NH₂, and C₆ H₅.

Another preferred set of organic groups which may be attached to thecarbon black are organic groups substituted with an ionic or anionizable group as a functional group. An ionizable group is one whichis capable of forming an ionic group in the medium of use. The ionicgroup may be an anionic group or a cationic group and the ionizablegroup may form an anion or a cation.

Ionizable functional groups forming anions include, for example, acidicgroups or salts of acidic groups. The organic groups, therefore, includegroups derived from organic acids. Preferably, when it contains anionizable group forming an anion, such an organic group has a) anaromatic group and b) at least one acidic group having a pKa of lessthan 11, or at least one salt of an acidic group having a pKa of lessthan 11, or a mixture of at least one acidic group having a pKa of lessthan 11 and at least one salt of an acidic group having a pKa of lessthan 11. The pKa of the acidic group refers to the pKa of the organicgroup as a whole, not just the acidic substituent. More preferably, thepKa is less than 10 and most preferably less than 9. Preferably, thearomatic group of the organic group is directly attached to the carbonblack. The aromatic group may be further substituted or unsubstituted,for example, with alkyl groups. More preferably, the organic group is aphenyl or a naphthyl group and the acidic group is a sulfonic acidgroup, a sulfinic acid group, a phosphonic acid group, or a carboxylicacid group. Examples of these acidic groups and their salts arediscussed above. Most preferably, the organic group is a substituted orunsubstituted sulfophenyl group or a salt thereof; a substituted orunsubstituted (polysulfo)phenyl group or a salt thereof; a substitutedor unsubstituted sulfonaphthyl group or a salt thereof; or a substitutedor unsubstituted (polysulfo)naphthyl group or a salt thereof. Apreferred substituted sulfophenyl group is hydroxysulfophenyl group or asalt thereof.

Specific organic groups having an ionizable functional group forming ananion (and their corresponding primary amines for use in a processaccording to the invention) are p-sulfophenyl (p-sulfanilic acid),4-hydroxy-3-sulfophenyl (2-hydroxy-5-amino-benzenesulfonic acid), and2-sulfoethyl (2-aminoethanesulfonic acid). Other organic groups havingionizable functional groups forming anions are shown in the examplesbelow.

Amines represent examples of ionizable functional groups that formcationic groups. For example, amines may be protonated to form ammoniumgroups in acidic media. Preferably, an organic group having an aminesubstituent has a pKb of less than 5. Quaternary ammonium groups (--NR₃⁺) and quaternary phosphonium groups (--PR₃ ⁺) also represent examplesof cationic groups. Preferably, the organic group contains an aromaticgroup such as a phenyl or a naphthyl group and a quaternary ammonium ora quaternary phosphonium group. The aromatic group is preferablydirectly attached to the carbon black. Quaternized cyclic amines, andeven quaternized aromatic amines, can also be used as the organic group.Thus, N-substituted pyridinium compounds, such as N-methylpyridyl, canbe used in this regard. Examples of organic groups include, but are notlimited to, (C₅ H₄ N)C₂ H₅ ⁺, C₆ H₄ (NC₅ H₅)⁺, C₆ H₄ COCH₂ N(CH₃)₃ ⁺, C₆H₄ COCH₂ (NC₅ H₅)⁺, (C₅ H₄ N)CH₃ ⁺, and C₆ H₄ CH₂ N(CH₃)₃ ⁺.

An advantage of the carbon black products having an attached organicgroup substituted with an ionic or an ionizable group is that the carbonblack product may have increased water dispersibility relative to thecorresponding untreated carbon black. As shown in the Examples, waterdispersibility of a carbon black product increases with the number oforganic groups attached to the carbon black having an ionizable group orthe number of ionizable groups attached to a given organic group. Thus,increasing the number of ionizable groups associated with the carbonblack product should increase its water dispersibility and permitscontrol of the water dispersibility to a desired level. It can be notedthat the water dispersibility of a carbon black product containing anamine as the organic group attached to the carbon black may be increasedby acidifying the aqueous medium.

Because the water dispersibility of the carbon black products depends tosome extent on charge stabilization, it is preferable that the ionicstrength of the aqueous medium be less than 0.1 molar. More preferably,the ionic strength is less than 0.01 molar.

When such a water dispersible carbon black product is prepared by aprocess of the invention, it is preferred that the ionic or ionizablegroups be ionized in the reaction medium. The resulting product solutionor slurry may be used as is or diluted prior to use. Alternatively, thecarbon black product may be dried by techniques used for conventionalcarbon blacks. These techniques include, but are not limited to, dryingin ovens and rotary kilns. Overdrying, however, may cause a loss in thedegree of water dispersibility.

In addition to their water dispersibility, carbon black products havingan organic group substituted with an ionic or an ionizable group mayalso be dispersible in polar organic solvents such as dimethylsulfoxide(DMSO), and formamide. In alcohols such as methanol or ethanol, use ofcomplexing agents such as crown ethers increases the dispersibility ofcarbon black products having an organic group containing a metal salt ofan acidic group.

Aromatic sulfides encompass another group of preferred organic groups.Carbon black products having aromatic sulfide groups are particularlyuseful in rubber compositions. These aromatic sulfides can berepresented by the formulas Ar(CH₂)_(q) S_(k) (CH₂)_(r) Ar' orA--(CH₂)_(q) S_(K) (CH₂)_(r) Ar" wherein Ar and Ar' are independentlysubstituted or unsubstituted arylene or heteroarylene groups, Ar" is anaryl or heteroaryl group, k is 1 to 8 and q and r are 0-4. Substitutedaryl groups would include substituted alkylaryl groups. Preferredarylene groups include phenylene groups, particularly p-phenylenegroups, or benzothiazolylene groups. Preferred aryl groups includephenyl, naphthyl and benzothiazolyl. The number of sulfurs present,defined by k preferably ranges from 2 to 4. Particularly preferredaromatic sulfide groups are bis-para-(C₆ H₄)--S₂ --(C₆ H₄)--and para-(C₆H₄)--S₂ --(C₆ H₅). The diazonium salts of these aromatic sulfide groupsmay be conveniently prepared from their corresponding primary amines, H₂N--Ar--S_(k) --Ar'--NH₂ or H₂ N--Ar--S_(k) --Ar".

Another preferred set of organic groups which may be attached to thecarbon black are organic groups having an aminophenyl, such as (C₆H₄)--NH₂, (C₆ H₄)--CH₂ --(C₆ H₄)--NH₂, (C₆ H₄)--SO₂ --(C₆ H₄)--NH₂.

Uses of the Carbon Black Products

The carbon black products of this invention may be used in the sameapplications as conventional carbon blacks. The organic groups attachedto the carbon black, however, can be used to modify and improve theproperties of a given carbon black for a particular use. If desiredthese organic groups attached to the carbon black may also be chemicallychanged using means known in the art into other groups for a particularuse. For example, an acid group can be converted to its salt or itsamide.

Carbon black products according to the invention have been prepared andevaluated in a number of end use applications. These uses include, forexample, plastic compositions, aqueous inks, aqueous coatings, rubbercompositions, paper compositions and textile compositions. The followingparagraphs describe these uses generally and examples of each are shownbelow.

The carbon black products of this invention may be used as pigments orcolorants in a plastic material. The carbon black products of theinvention can also be used to impart conductivity to a plastic material.The carbon black products of the invention may give an increased rate ofdispersion or improved quality of dispersion over the correspondinguntreated carbon blacks. These improvements offer an economic advantagein plastic manufacture and in value of the finished product,respectively. As shown in Examples 47-62, using carbon black products ofthe invention may improve impact strength of the plastic. Thus, theinvention relates to an improved plastic composition comprising aplastic and a carbon black, the improvement comprising the use of acarbon black product according to the invention.

As with conventional carbon blacks, the carbon black products can beused with a variety of plastics, including but not limited to plasticsmade from thermoplastic resins, thermosetting resins, or engineeredmaterials, for example, composites. Typical kinds of thermoplasticresins include: (1) acrylonitrile-butadiene-styrene (ABS) resins; (2)acetals; (3) acrylics; (4) cellulosics; (5) chlorinated polyethers; (6)fluorocarbons, such as polytetrafluoroethylene (TFE),polychlorotrifluoroethylene (CTFE), and fluorinated ethylene propylene(FEP); (7) nylons (polyamides); (8) polycarbonates; (9) polyethylenes(including copolymers); (10) polypropylenes (including copolymers); (11)polystyrenes; (12) vinyls (polyvinyl chloride); (13) thermoplasticpolyesters, such as polyethylene terephthalate or polybutyleneterephthalate; (14) polyphenylene ether alloys; and blends and alloys ofthe above with rubber modifiers. Typical thermosetting resins include:(1) alkyds; (2) allylics; (3) the aminos (melamine and urea); (4)epoxies; (5) phenolics; (6) polyesters; (7) silicones; and (8)urethanes.

Generally, the carbon black product is added like any other pigment tothe plastic used to form a plastic premix. This can be done, forexample, in a dry mix or a melt stage. The carbon black products of theinvention may be used in combination with other conventional additivesin plastic compositions. According to the invention, the term plasticcomposition includes, but is not limited to, any plastic material,article, goods, surface, fabric, sheet, and the like For example,plastic materials include automotive parts, siding for homes, liners forswimming pools, roofing materials, packaging materials, and any varietyof other household or industrial items.

The carbon black products of this invention are also useful in aqueousink formulations. The water-dispersible carbon black products discussedabove are particularly preferred for this use. Thus, the inventionprovides an improved ink composition comprising water and a carbonblack, the improvement comprising the use of a carbon black productaccording to the invention. Other known aqueous ink additives may beincorporated into the aqueous ink formulation.

In general, an ink consists of four basic components: (1) a colorant orpigment, (2) a vehicle or varnish which functions as a carrier duringprinting, (3) additives to improve printability drying, and the like,and (4) solvents to adjust viscosity, drying and the compatibility ofthe other ink components. For a general discussion on the properties,preparation and uses of aqueous inks, see The Printing Manual, 5th Ed.,Leach et al, Eds. (Chapman and Hall, 1993). Various aqueous inkcompositions are also disclosed, for example, in U.S. Pat. Nos.2,833,736, 3,607,813, 4,104,833, 4,308,061, 4,770,706, and 5,026,755.

The carbon black products of the invention, either as predispersion oras a solid, can be incorporated into an aqueous ink formulation usingstandard techniques. Use of a water dispersible carbon black product ofthe invention provides a significant advantage and cost savings byreducing or eliminating the milling steps generally used with otherconventional carbon blacks.

Flexographic inks represent a group of aqueous ink compositions.Flexographic inks generally include a colorant, a binder, and a solvent.The carbon black products of the invention, particularly thewater-dispersible carbon products, are useful as flexographic inkcolorants. Example 101 shows the use of a carbon black product of theinvention in an aqueous flexographic ink formulation.

The carbon black products of the invention can be used in aqueous newsinks. For example, an aqueous news ink composition may comprise water,the carbon black products of the invention, a resin and conventionaladditives such as antifoam additives or a surfactant.

The carbon black products of the invention may also be used in aqueouscoating compositions such as paints or finishes. The use of the waterdispersible carbon black products discussed above in such coatingcompositions is preferred. Thus, an embodiment of the invention is animproved aqueous coating composition comprising water, resin and acarbon black, the improvement comprising the use of a carbon blackproduct according to the invention. Other known aqueous coatingadditives may be incorporated the aqueous coating compositions. See, forexample, McGraw-Hill Encyclopedia of Science & Technology, 5th Ed.(McGraw-Hill, 1982). See also U.S. Pat. Nos. 5,051,464, 5,319,044,5,204,404, 5,051,464, 4,692,481, 5,356,973, 5,314,945, 5,266,406, and5,266,361.

The carbon black products of the invention, either as a predispersion oras a solid, can be incorporated into an aqueous coating compositionusing standard techniques. Use of a water dispersible carbon blackproduct provides a significant advantage and cost savings by reducing oreliminating the milling steps generally used with other conventionalcarbon blacks. Examples 102 and 103 below show the use of carbon blackproducts according to the invention in aqueous automotive topcoatformulations.

The carbon black products of the invention may also be used in papercompositions. Preferred carbon black products for this use are the waterdispersible carbon black products discussed above. Accordingly, theinvention relates to an improved paper product comprising paper pulp anda carbon black, the improvement comprising the use of a carbon blackaccording to the invention.

The carbon black products of the invention, either as a solid or apredispersion, can be incorporated into paper pulp using standardpapermaking techniques as with conventional carbon blacks. Use of awater dispersible carbon black product discussed above may provide asignificant advantage and cost savings by reducing or eliminating thesteps generally used to disperse other conventional carbon blacks.Example 100 shows a paper product using a carbon black product accordingto the invention.

The paper products of the invention may incorporate other known paperadditives such as sizing agents, retention aids, fixatives, fillers,defoamers, deflocculating agents, and the like. Advantageously, thewater dispersible carbon black products discussed above are retainedmore efficiently at low loading levels when compared to the untreatedcarbon black when retention aids and acidic or alkaline sizing agentsare used.

The carbon black products of the invention may also be used, as withconventional carbon blacks, as pigments, fillers, and reinforcing agentsin the compounding and preparation of rubber compositions. Accordingly,the invention relates to an improved rubber composition containingrubber and a carbon black, the improvement comprising the use of acarbon black product according to the invention. The properties of thecarbon black are important factors in determining the performance of therubber composition containing a carbon black.

Carbon blacks, for example, are useful in the preparation of rubbervulcanizates such as those in tires. It is generally desirable in theproduction of tires to utilize carbon blacks which produce tireswith-satisfactory abrasion resistance and hysteresis performance. Thetreadwear properties of a tire are related to abrasion resistance. Thegreater the abrasion resistance, the greater the number of miles thetire will last without wearing out. The hysteresis of a rubber compoundmeans the difference between the energy applied to deform a rubbercompound, and the energy released as the rubber compound recovers to itsinitial undeformed state. Tires with lower hysteresis values reducerolling resistance and therefore are able to reduce the fuel consumptionof the vehicle utilizing the tire. Thus, it is particularly desirable tohave carbon black products capable of imparting greater abrasionresistance and lower hysteresis in tires.

The carbon black products of this invention are useful in both naturaland synthetic rubber compositions or mixtures of natural and syntheticrubbers. Carbon black products containing aromatic sulfides as theorganic group, which are discussed above, are prefered for this use.Particularly preferred for use in rubber compositions are carbon blackproducts having an attached aromatic sulfide organic group of theformula --(C₆ H₄)--S_(k) --(C₆ H₄)--, where k is an integer from 1 to 8,and more preferably where k ranges from 2 to 4. The carbon blackproducts of the invention can be used in rubber compositions which aresulfur-cured or peroxide-cured.

The carbon black products may be mixed with natural or synthetic rubbersby normal means, for example by milling. Generally, amounts of thecarbon black product ranging from about 10 to about 250 parts by weightcan be used for each 100 parts by weight of rubber in order to impart asignificant degree of reinforcement. It is, however, preferred to useamounts varying from about 20 to about 100 parts by weight of carbonblack per 100 parts by weight of rubber and especially preferred is theutilization of from about 40 to about 80 parts of carbon black per 100parts of rubber.

Among the rubbers suitable for use with the present invention arenatural rubber and its derivatives such as chlorinated rubber. Thecarbon black products of the invention may also be used with syntheticrubbers such as: copolymers of from about 10 to about 70 percent byweight of styrene and from about 90 to about 30 percent by weight ofbutadiene such as copolymer of 19 parts styrene and 81 parts butadiene,a copolymer of 30 parts styrene and 70 parts butadiene, a copolymer of43 parts styrene and 57 parts butadiene and a copolymer of 50 partsstyrene and 50 parts butadiene; polymers and copolymers of conjugateddienes such as polybutadiene, polyisoprene, polychloroprene, and thelike, and copolymers of such conjugated dienes with an ethylenicgroup-containing monomer copolymerizable therewith such as styrene,methyl styrene, chlorostyrene, acrylonitrile, 2-vinyl-pyridine, 5-methyl2- vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine,alkyl-substituted acrylates, vinyl ketone, methyl isopropenyl ketone,methyl vinyl either, alphamethylene carboxylic acids and the esters andamides thereof such as acrylic acid and dialkylacrylic acid amide; alsosuitable for use herein are copolymers of ethylene and other high alphaolefins such as propylene, butene-1 and pentene-1.

The rubber compositions of the present invention can therefore containan elastomer, curing agents, reinforcing filler, a coupling agent, and,optionally, various processing aids, oil extenders, and antidegradents.In addition to the examples mentioned above, the elastomer can be, butis not limited to, polymers (e.g., homopolymers, copolymers, andterpolymers) manufactured from 1,3 butadiene, styrene, isoprene,isobutylene, 2,3-dimethyl-1,3 butadiene, acrylonitrile, ethylene,propylene, and the like. It is preferred that these elastomers have aglass transition point (Tg), as measured by DSC, between -120° C. and 0°C. Examples of such elastomers include poly(butadiene),poly(styrene-co-butadiene), and poly(isoprene).

Advantageously, the carbon black products of the present invention canimpart improved abrasion resistance and/or reduced hysteresis to rubbercompositions containing them. Examples 104-116 show the use of carbonblack products of the invention in various rubber compositions andvarious properties of those compositions.

The carbon black products of this invention may also be used to colorfibers or textiles. Preferred carbon black products for this use are thewater dispersible carbon black products discussed above. Accordingly,the invention relates to improved fiber and textile compositionscomprising a fiber or textile and a carbon black, the improvementcomprising the use of a carbon black according to the invention. Fiberssuitable for use comprise natural and synthetic fibers such as cotton,wool, silk, linen, polyester and nylon. Textiles suitable for usecomprise natural and synthetic fibers such as cotton, wool, silk, linen,polyester and nylon. Preferably natural fibers and textiles comprisingcotton, wool, silk and linen are used.

The carbon black-products of the present invention may be colored bymeans known in the art to color fibers and textiles with, for example,direct and acid dyes. For a general discussion of coloring with dyes,see Kirk-Othmer Encyclopedia of Chemical Technology, Vol 8 pp 280-350"Dyes, Application and Evaluation" (John Wiley and Sons, 1979). Use of awater dispersible carbon black product discussed above provides a methodfor coloring these materials with a lightfast colorant.

The following examples are intended to illustrate, not limit, theclaimed invention.

EXAMPLES

Analytical Methods

Unless otherwise specified, BET nitrogen surface areas obtainedaccording to ASTM D-4820 are used for surface area measurements. CTABareas and iodine numbers are used occasionaly and were obtainedaccording to ASTM D-3765 and D-1510, respectively. DBPA data wereobtained according to ASTM D-2414.

Volatile content was determined as follows. A carbon black sample wasdried to constant weight at 125° C. A 45 mL sample of the dry carbonblack was placed in a covered 50 mL crucible that had been dried at 950°C. and heated in a muffle furnace for 7 minutes at 950° C. The volatilecontent is expressed as the percentage of weight lost by the carbonsample.

The following procedure was used in various Examples below to determinethe aqueous residue of carbon black products according to this inventionand untreated carbon blacks. The carbon black product (5 g) was shakenwith 45 g of water for 5 minutes. The resulting dispersion was pouredthrough a screen and rinsed with water until the washings werecolorless. A 325 mesh screen was used unless indicated otherwise. Afterdrying the screen, the weight of residue on the screen was determinedand expressed as a percentage of the carbon black product used in thetest.

For the Examples relating to rubber compositions, modulus, tensilestrength, and elongation were determined according to ASTM D-412. ShoreA hardness was determined according to ASTM D-2240-86.

The abrasion data on the rubber compositions were determined using anabrader which is based on a Lambourn type machine. Abrasion rates (cubiccentimeter/centimeter travel) were measured at 14% and 21% slip. Theslip is based on the relative velocity between the sample wheel andgrindstone. In the following examples, the abrasion index is the ratioof the abrasion rate of a control compositon divided by the abrasionrate of a rubber compostion prepared with a carbon black product of theinvention.

Tan δ was measured with a Rheometrics Dynamic Spectrometer Model RDS-2at a constant frequency of 10 Hz, a constant temperature, and in theshear mode of strain. Strain sweeps were run from 0.2% to 120% DSA.Measurements were taken at five points per decade and the maximum Tan δwas reported.

Bound rubber was determined as follows: A 0.5 g sample of an uncuredrubber composition containing a rubber and a known amount of a carbonblack was placed in a wire cage and submerged in toluene at roomtemperature. After standing for one day, the sample was placed in freshtoluene, and allowed to stand for three additional days at roomtemperature. The sample was then removed, dried in an oven, and weighed.The weight of the carbon black was subtracted from weight of the samplebefore and after toluene treatment to give a value for the amount ofrubber in each sample. The weight of the sample after toluene treatment,adjusted for the weight of the carbon black and other insolubleingredients in the composition, represents the amount of insolublerubber remaining. Bound rubber was expressed as the percentage of theweight of insoluble rubber in the sample after standing in tolueneversus the amount of rubber in the original sample.

Example 1

Preparation of a carbon black product with preformed diazonium salt

This example illustrates the preparation of a carbon black product ofthe present invention. A pelleted carbon black with a surface area of230 m² /g and a DBPA of 64 ml/100 g was used. An aqueous solution of4-bromobenzenediazonium chloride was prepared from 0.688 g of4-bromoaniline, 0.300 g of sodium nitrite, 1.38 g of concentrated HCland 2.90 g of water at <5° C. This solution was added to a suspension of10 g of the pelleted carbon black in 60 g of water at room temperature.Bubbles were released. After stirring for 60 minutes, the resultingcarbon black product was removed by filtration, washed with water andsubjected to Soxhlet extraction with tetrahydrofuran (THF) overnight.Analysis of the carbon black product after extraction showed that itcontained 2.49% bromine, compared to <0.01% for the untreated pelletedcarbon black prior to use in this example. This corresponds to 78% ofthe bromophenyl groups being attached to the carbon black product.Therefore, the carbon black product has 0.31 mmol/g of attachedbromophenyl groups.

Examples 2-4

Preparation of a carbon black product with preformed diazonium salt

These examples illustrate additional methods for the preparation ofcarbon black products of the present invention. The pelleted carbonblack used in Example 1 was used in Examples 2-4. An aqueous solution of4-bromobenzenediazonium chloride was prepared from 0.688 g of4-bromoaniline, 0.300 g of sodium nitrite, 1.38 g of concentrated HCland 2.90 g of water at <5° C. This solution was added to a suspension of10 g of the pelleted carbon black in 60.5 g of a 0.826% NaOH solution atthe temperature indicated. Bubbles were released. After stirring for thetime indicated in the following table, the resulting carbon blackproduct was removed by filtration, washed with water and subjected toSoxhlet extraction with THF overnight. Bromine analysis of the productafter extraction showed that a substantial fraction of the bromophenylgroups had been attached to the carbon black product. This shows thatthe preparation of carbon black products according to the invention canbe carried our at different times, temperatures and pHs.

    ______________________________________                                                                      Portion of                                                                            Bromophenyl                             Exam- Tempera- Time,          bromophenyl                                                                           groups,                                 ple   ture, C. min.   Bromine, %                                                                            retained, %                                                                           mmol/g                                  ______________________________________                                        2     <5       5      1.88    59      0.24                                    3     <5       60     2.15    67      0.27                                    4     Ambient  60     2.45    77      0.31                                    ______________________________________                                    

Example 5

Preparation of a carbon black product with a diazonium salt generated insitu

This example further illustrates the preparation of a carbon blackproduct of the present invention. A fluffy carbon black with a surfacearea of 560 m2/g, a DBPA of 90 ml/100 g and a volatile content of 9.5%was used. Fifty grams of the fluffy carbon black were added to asolution of 8.83 g of sulfanilic acid dissolved in 420 g of water. Theresulting suspension was cooled to room temperature. Nitrogen dioxide(5.16 g) was dissolved in 30 g of ice cold water, and then added to thefluffy carbon black suspension over a period of several minutes andstirred rapidly, to produce 4-sulfobenzenediazonium inner salt in situ,which reacts with the fluffy carbon black. The resulting dispersion wasdried in an oven at 125° C., leaving only the carbon black product. Thecarbon black product contained 1.94% sulfur after Soxhlet extractionwith ethanol overnight, compared to 0.24% sulfur for the untreatedcarbon black. This corresponds to attaching 52% of the p-C6H4SO3--groups to the carbon black product. Therefore, the carbon black producthad 0.53 mmol/g of attached p-C₆ H₄ SO₃ -- groups.

Example 6

Preparation of a carbon black product

This example illustrates another method for the preparation of a carbonblack product of the present invention . Sulfanilic acid (2.13 g) wasdissolved in 90 g of water with stirring and heating. Ten grams of acarbon black with a CTAB surface area of 350 m2/g and a DBPA of 120ml/100 g were added. The mixture was cooled to room temperature andisobutyl nitrite (1.27 g) was added. Bubbles were released.4-Sulfobenzene diazonium hydroxide inner salt was generated in situ andit reacted with the carbon black. The mixture was stirred for 30minutes, and dried in an oven at 125° C. A sample of the resultingcarbon black product that had been subjected to Soxhlet extraction withethanol overnight contained 2.02% sulfur, compared to 0.5% for theuntreated carbon black. Therefore, the carbon black product had 0.48mmol/g of attached p-C₆ H₄ SO₃ -- groups.

Example 7

Preparation of a carbon black product in an aprotic solvent

This example illustrates the preparation of a treated carbon blackproduct of the present invention in an aprotic solvent. A 0.1M solutionof tetrabutylammonium hexafluorophosphate in anhydrous acetonitrile wasprepared and allowed to stand overnight over 3A molecular sieves. A 5.4%solution of chlorobenzenediazonium hexafluorophosphate in anhydrousacetonitrile was prepared and allowed to stand overnight over 3Amolecular sieves. A carbon black with a surface area of 230 m2/g and aDBPA of 70 ml/100 g was dried at 150° C. under nitrogen for 4 hours. Thecarbon black (10 g) was stirred into 80 mL of the tetrabutylammoniumhexafluorophosphate solution. The diazonium solution (21 g) was added,and the mixture was stirred for four hours. The carbon black product wasrecovered by filtration and was washed with anhydrous acetonitrile. Alloperations up to this point were carried out in a dry box under an argonatmosphere. A sample of the carbon black product that was subjected toSoxhlet extraction overnight with THF and dried had a chlorine contentof 0.76%, compared to 0.02% for the untreated carbon black. Therefore,the carbon black product had 0.21 mmol/g of attached chlorophenylgroups.

Example 8

Preparation of a carbon black product in an aprotic solvent

This example illustrates the preparation of a treated carbon blackproduct of the present invention in an aprotic solvent. A carbon blackwith a surface area of 230 m2/g and a DBPA of 70 ml/100 g was heated at950° C. under nitrogen for one hour. A 0.1M solution oftetrabutylammonium tetrafluoroborate in anhydrous benzonitrile wasprepared and allowed to stand overnight over 3A molecular sieves. Usingglassware dried at 160° C. under argon, the carbon black (6 g) wasstirred into 50 mL of the tetrabutylammonium tetrafluoroborate solution.4-Bromobenzenediazonium tetrafluoroborate was added, and the mixture wasstirred for 15 minutes. The carbon black product was recovered byfiltration and was washed twice with anhydrous benzonitrile and twicewith hexanes. Except for the initial drying of the carbon black, alloperations up to this point were carried out under an argon atmospherein a dry box. A sample of the carbon black product that was subjected toSoxhlet extraction overnight with THF and dried had a bromine content of0.85%, compared to <0.01% for the untreated carbon black. Therefore, thecarbon black product had 0.11 mmol/g of attached bromophenyl groups.

Example 9

Preparation of a carbon black product with a diazonium salt generated insitu

This example illustrates another method for the preparation of a carbonblack product of the present invention. A fluffy carbon black with asurface area of 560 m2/g, a DBPA of 90 ml/100 g and a volatile contentof 9.5% was used. Fifty grams of the fluffy carbon black were added to asolution of 8.83 g of sulfanilic acid dissolved in 420 g of water. Theresulting suspension was cooled to 30° C. and 4.6 g of concentratednitric acid was added. An aqueous solution containing 3.51 g of sodiumnitrite was then added gradually with stirring, forming4-sulfobenzenediazonium hydroxide inner salt in situ, which reacts withthe fluffy carbon black. The resulting product was dried in an oven at125° C., leaving the carbon black product. The carbon black productcontained 1.97% sulfur after Soxhlet extraction with ethanol overnight,compared to 0.24% sulfur for the untreated fluffy carbon black. Thiscorresponds to attaching 53% of the p-C₆ H₄ SO₃ -- groups to the carbonblack product. Therefore, the carbon black product had 0.54 mmol/g ofattached p-C₆ H₄ SO₃ -- groups.

Example 10

Preparation of a carbon black product with an aliphatic diazonium salt

This example shows another method for the preparation of a carbon blackproduct of the present invention. A fluffy carbon black with a surfacearea of 230 m2/g and a DBPA of 70 ml/100 g was used. Twenty grams ofthis black were added to a solution of 4.9 g of 2-aminoethanesulfonicacid in 180 g of water. Concentrated nitric acid (4.32 g) was added. Asolution of 3.33 g of sodium nitrite in 15 g of water was added slowlywith stirring, forming 2-sulfoethanediazonium nitrate in situ, whichreacted with the fluffy carbon black. A large quantity of bubblesevolved. The product was dried in an oven at 135° C., leaving a carbonblack product. The resulting carbon black product contained 1.68% sulfurafter Soxhlet extraction with ethanol overnight, compared to 0.4% forthe untreated fluffy carbon black. This corresponds to attaching 20%of.the C₂ H₄ SO₃ -- groups to the carbon black product. Therefore, thecarbon black product had 0.40 mmol/g of attached C₂ H₄ SO₃ -- groups.

Example 11

Preparation of a carbon black product with a benzyldiazonium salt

This example shows another method for the preparation of a carbon blackproduct of the present invention. A suspension of 0.676 g of4-bromobenzyl amine, 0.60 g of concentrated HCl, 30 g of water and 10.22g of the untreated carbon black used in Example 7 was prepared in an icebath. An aqueous solution containing 0.269 g of sodium nitrite was addedand the resulting suspension was stirred for 15 minutes, forming4-bromophenylmethanediazonium chloride in situ, which reacted with theuntreated carbon black. The product was filtered off, and was subjectedto Soxhlet extraction with THF overnight. The resulting carbon blackproduct contained 0.26% bromine, compared to <0.01% for the untreatedcarbon black product. This shows that 9% of the bromobenzyl groups usedin the example became attached to the carbon black product. Therefore,the carbon black product had 0.031 mmol/g of attached bromobenzylgroups.

Example 12

Preparation of a carbon black product

This example illustrates the preparation of a carbon black product ofthe present invention. Ten grams of a carbon black with a surface areaof 230 m2/g and a DBPA of 70 ml/100 g was added to a stirring solutionof 0.8 g 4-bromobenzamide and 90 ml of acetone in 90 g of water.Concentrated HCl (0.87 g) was added followed by 0.33 g of NaNO₂. BrC₆ H₄CON₂ ⁺ was formed in situ, which reacted with the carbon black. Afterstirring for 30 minutes, the mixture was allowed to stand overnight andwas then dried in an oven at 125° C. A sample of the product that hadbeen subjected to Soxhlet extraction with THF overnight and driedcontained 0.22% bromine, compared to <0.01% bromine for the unreactedcarbon black.

Example 13

Preparation of a carbon black product with a preformed diazonium salt ina pin pelletizer

This example shows another method for the preparation of a carbon blackproduct of the present invention. A pin pelletizer was charged with 400g of a fluffy carbon black with a surface area of 80 m2/g and a DBPA of85 ml/100 g. A cold suspension of 4-sulfobenzenediazonium hydroxideinner salt prepared from 27.1 g of the sodium salt of sulfanilic acid,10.32 g of sodium nitrite, 29.0 g of concentrated HCl and 293.5 g ofwater and was added to the pelletizer. After pelletizing for 2 minutes,the sample was removed and dried at 115° C. to constant weight. Soxhletextraction with ethanol overnight gave a carbon black product containing1.1% sulfur, compared against 0.8% for the untreated carbon black. Thisshows that 27% of the p-C₆ H₄ SO₃ -- groups were attached to the carbonblack product. Therefore, the carbon black product had 0.09 mmol/g ofattached p-C₆ H₄ SO₃ -- groups.

Example 14

Preparation of a carbon black product in a pin pelletizer with adiazonium salt generated in situ

This example illustrates another method for preparing a carbon blackproduct of the present invention. A pin pelletizer was charged with 200g of a carbon black with a CTAB surface area of 350 m2/g and a DBPA of120. A solution of 44.2 g of sodium sulfanilate in 95 g of water at 70°C. was added and the pelletizer was run for one minute. Twenty grams ofwater was added followed by 39.6 g of concentrated nitric acid. Thepelletizer was run for an additional minute. Twenty grams of water wasadded followed by a solution of 16.76 g of sodium nitrite in 35 g ofwater, forming 4-sulfobenzenediazonium hydroxide inner salt in situ,which reacted with the carbon black. After running the pelletizer forfive minutes, a solution of 11.22 g of sodium hydroxide in 35 g of waterwas added. The pelletizer was run for an additional two minutes and theresulting a carbon black product was subsequently dried. Soxhletextraction with ethanol overnight gave a carbon black product with 3.3%sulfur, compared against 0.5% for the untreated carbon black. This showsthat 77% of the p-C6H4SO3-- groups were attached to the carbon blackproduct. Therefore, the carbon black product had 0.88 mmol/g of attachedp-C₆ H₄ SO₃ -- groups.

Example 15

Preparation of a carbon black product in a pin pelletizer with adiazonium salt generated in situ

This example further illustrates the preparation of a carbon blackproduct of the present invention. A pin pelletizer was charged with 200g of a carbon black product with a surface area of 560 m2/g, a DBPA of90 ml/100 g and a volatile content of 9.5%. Water (60 g), concentratednitric acid (25.2 g), sulfanilic acid (40.4 g) and a solution of 19.7 gof sodium nitrite in 35 g of water were added successively; thepelletizer was run for one minute after each addition.4-Sulfobenzenediazonium hydroxide inner salt was generated in situ, andit reacted with the carbon black. After standing for five minutes, theresulting carbon black product was dried at 125° C. A sample of thecarbon black product was subjected to Soxhlet extraction with ethanolovernight. It contained 2.15% sulfur compared to 0.24% for the untreatedcarbon black. This shows that 51% of the p-C₆ H₄ SO₃ -- groups wereattached to the carbon black product. Therefore, the carbon blackproduct had 0.60 mmol/g of attached p-C₆ H₄ SO₃ -- groups.

Example 16

Preparation of a carbon black product in a pelletizer with a diazoniumsalt generated in situ

This example illustrates another method for the preparation of a carbonblack product of the present invention. A carbon black (200 g) with aCTAB surface area of 350 m2/g and a DBPA of 120 ml/100 g and 42.4 gsulfanilic acid were placed in a pin pelletizer. After mixing for 40seconds, a solution of 20.7 NaNO₂ in 150 g of water was then added.4-sulfobenzene diazonium hydroxide inner salt was formed in situ, whichreacted with the carbon black. After mixing for 45 seconds, theresulting carbon black product was dried in an oven at 120° C. A sampleof the product that had been subjected to Soxhlet extraction overnightwith ethanol contained 3.47% sulfur, compared to 0.5% sulfur for theuntreated carbon black product. Therefore, the carbon black product has0.93 mmol/g of attached p-C₆ H₄ SO₃ -- groups.

Example 17

Preparation of a carbon black product in a continuous pin pelletizerwith a diazonium salt generated in situ

This example illustrates another method for preparing a carbon blackproduct of the present invention. A carbon black with a CTAB surfacearea of 133 m2/g and a fluffy DBPA of 190 ml/100 g is introduced into acontinuously operating pin pelletizer at a rate of 100 parts by weightper hour. Simultaneously, a 30% solution of sodium nitrite in water anda suspension containing 5.43% concentrated nitric acid, 8.72% sulfanilicacid and 85.9% water are introduced into the pelletizer. The sodiumnitrite solution is introduced at 16 parts by weight per hour and thesuspension is added at 112 parts by weight per hour.4-Sulfobenzenediazonium hydroxide inner salt was generated in situ andit reacted with the carbon black in the pelletizer. The material leavingthe pelletizer was the carbon black product. The carbon black productwas dried at 125° C. A sample of the carbon black product that had beensubjected to Soxhlet extraction with ethanol overnight contained 1.70%sulfur, compared to 0.42% for the untreated carbon black. Therefore, thecarbon black product had 0.40 mmol/g of attached p-C₆ H₄ SO₃ -- groups.

Example 18

Preparation of a carbon black product with a diazonium salt generated insitu

This example shows another method for preparing a carbon black productof the present invention. In this example, the acid for thediazotization reaction comes from the amine forming the diazonium salt,sulfanilic acid. As a result, no additional acid was required.Sulfanilic acid (2.12 g) was dissolved in 90 g water at 70° C. Thesolution was added to 10 g of a carbon black with a CTAB surface area of350 m2/g and a DBPA of 120 ml/100 g, and cooled to room temperature. Asolution of 1.04 g NaNO₂ in 10 g water was added with stirring.4-Sulfobenzenediazonium hydroxide inner salt was generated in situ andit reacted with the carbon black to form the carbon black product. Afterstirring for 30 minutes, the resulting dispersion was dried in an ovenat 120° C. A sample of the carbon black product that had been subjectedto Soxhlet extraction with ethanol overnight contained 3.19% sulfur,compared to 0.5% for the untreated carbon black product. Therefore, thecarbon black product had 0.84 mmol/g of attached p-C₆ H₄ SO₃ -- groups.

Example 19

Preparation of a carbon black product with a diazonium salt generated insitu

This example illustrates another method for the preparation of a carbonblack product of the present invention. In this example, the acid forthe diazotization reaction comes from the amine forming the diazoniumsalt, sulfanilic acid. As a result, no additional acid was required. Acarbon black (10 g) with a CTAB surface area of 350 m2/g and a DBPA of120 ml/100 g was added to a boiling solution of 2.12 g sulfanilic acidin 90 g of water. A solution of 1.04 g of NaNO₂ in 10 g water was addedcautiosly. 4-Sulfobenzene diazonium hydroxide inner salt was formed insitu, which reacted with the carbon black. After stirring for about 20min, the resulting dispersion was dried in an oven at 120° C. A sampleof the product that had been subjected to Soxhlet extraction overnightwith ethanol contained 3.16% sulfur, compared to 0.5% sulfur for theuntreated carbon black. Therefore, the carbon black product had 0.83mmol/g of attached p-C₆ H₄ SO₃ -- groups.

Examples 20-30

Aqueous dispersibility of carbon black products

These examples show that carbon black products of the present inventiondescribed in some earlier examples are more readily dispersed in waterthan the corresponding untreated carbon black.

    ______________________________________                                                 Carbon       Residue of Residue of                                            Black        Carbon Black                                                                             untreated                                    Example  Product      Product, % control, %                                   ______________________________________                                        20       Example 5    3.0        6                                            21       Example 6    0.2        97                                           22       Example 9    0.12       6                                            23       Example 10   2.1        94                                           24       Example 13   0.07       81                                           25       Example 14   0.3        97                                           26       Example 15   0.26       6                                            27       Example 16   0.6        97                                           28       Example 17   0.02       36                                           29       Example 18   0.04       97                                           30       Example 19   0.01       97                                           ______________________________________                                    

Examples 31-34

Preparation and aqueous dispersibility of carbon black products

These examples show that carbon black products prepared using severaldifferent diazonium salts are more readily dispersed in water than arethe corresponding untreated carbon blacks. In all cases, the untreatedcarbon black used for treatment has a surface area of 230 m2/g and aDBPA of 70 ml/100 g. To prepare the carbon black product, an anilinederivative was dissolved in warm water, the untreated carbon black (CB)was added and the mixture was cooled to room temperature. ConcentratedHCl was added and then a solution of sodium nitrite in water was added,forming a diazonium salt in situ, which reacts with the untreated carbonblack. After stirring for 15 minutes, the resulting dispersions weredried in an oven at 125° C. Residues were determined using the methoddescribed above. The amounts of each component and results are shown inthe following table. The untreated carbon black had a residue of 94%.

    ______________________________________                                                       Aniline                                                        Exam- Aniline  derivative                                                                             HCl  NaNO2 CB   H20  Resi-                            ple   derivative                                                                             g        g    g     g    g    due %                            ______________________________________                                        31    5-Amino 2                                                                              1.89     1.18 0.85  10.0 100  0.06                                   Hydroxy                                                                       benzene                                                                       sulfonic                                                                      acid                                                                    32    2-Amino- 1.73     1.18 0.82  10.0 67   0.14                                   benzene                                                                       sulfonic                                                                      acid                                                                    33    3-Amino- 1.72     1.18 0.84  10.4 77   0.16                                   benzene                                                                       sulfonic                                                                      acid                                                                    34    4-Amino  2.94     2.60 0.83  10.0 71   2.0                                    azoben-                                                                       zene-4'sul-                                                                   fonic acid,                                                                   Na salt                                                                 Com-  Untreated                                                                              --       --   --    --   --   94                               para-                                                                         tive                                                                          ______________________________________                                    

Examples 35-38

Preparation and dispersibility of carbon black products

These examples show additional carbon black products that are preparedusing different diazonium salts and that are more readily dispersible inwater than the corresponding untreated carbon black. All of theseexamples use naphthyl diazonium salts. In all cases, a carbon black witha surface area of 230 m2/g and a DBPA of 70 ml/100 g was used. Asolution of 7 mmol of the naphthylamine and 0.42 g NaNO₂ in 10.83 gwater was cooled to <5° C. The diazonium salt was formed by the additionof a cold (5° C.) solution of 1.63 g concentrated HCl in 1.63 g water,maintaining the temperature at <5° C. The reaction product was added toa stirring slurry of 10 g of the untreated carbon black in 90 g ofwater. After stirring for an additional 10 minutes, the dispersion wasdried, leaving the carbon black product. Samples of the carbon blackproducts that had been subjected to Soxhlet extraction overnight withethanol were analyzed for sulfur to determine the number of attachednaphthyl groups.

    ______________________________________                                                                     Substituted                                                                   naphthyl                                                 Naphthylamine        groups,                                          Example derivative Sulfur %  mmol/g  Residue %                                ______________________________________                                        35      Sodium 5-  2.15      0.51    <0.01                                            amino-2-                                                                      naphthalene                                                                   sulfonate                                                             36      4-Amino-5- 2.77      0.35    0.02                                             hydroxy-2,7-                                                                  naphthalene                                                                   disulfonic                                                                    acid, mono                                                                    potassium                                                                     salt                                                                  37      7-Amino-1,3-                                                                             3.09      0.40    0.01                                             naphthalene                                                                   disulfonic                                                                    acid, mono                                                                    potassium                                                                     salt                                                                  38      Sodium 4-  1.79      0.40    0.33                                             amino-1-                                                                      naphthalene                                                                   sulfonate                                                             Compara-                                                                              Untreated  0.5       --      94                                       tive                                                                          ______________________________________                                    

Example 39

Preparation and aqueous dispersibility of a carbon black product

This example illustrates another method for the preparation of a carbonblack product of the present invention and illustrates that this carbonblack product was more readily dispersible in water than is thecorresponding untreated carbon black. 7-Amino-1,3-naphthalenedisulfonicacid (1.5 g) was dissolved in 90 g warm water. Ten grams of a carbonblack with a surface area of 230 m2/g and a DBPA of 70 ml/100 g wasadded, and the mixture was cooled to room temperature. A solution of0.42 g NaNO₂ in 5 g water was added with stirring. The diazonium saltwas formed in situ and reacted with the carbon black. Bubbles werereleased. The resulting dispersion was dried in an oven at 125° C.,giving the carbon black product. The carbon black product had a residueof 0.85%, compared to 94% for the untreated carbon black.

Example 40

Preparation and aqueous dispersibility of a carbon black product

This example shows that a carbon black product prepared using anotherdiazonium salt was more readily dispersible in water than thecorresponding untreated carbon black. The carbon black used fortreatment had a surface area of 230 m2/g and a DBPA of 70 ml/100 g.5-Amino-2-hydroxy-3-sulfobenzoic acid (2.33 g), 10 g of carbon black and100 g of water were mixed in an ice bath. Cold concentrated HCl (1.18 g)was added, followed gradually by 0.85 g NaNO₂. The diazonium salt wasformed in situ, and reacted with the carbon black. After stirring for 15minutes, the resulting dispersion was dried in an oven at 125° C. toprovide the carbon black product. The 325 mesh residue of the resultingcarbon black product was 0.1%, compared to 94% for the untreated carbonblack.

Example 41

Preparation and aqueous dispersibility of a carbon black product

This example shows that a carbon black product prepared with anotherdiazonium salt was more readily dispersible in water than thecorresponding untreated carbon black. The procedure of Example 40 wasfollowed in all respects, except that 4-amino-2'-nitro-4'-sulfodiphenylamine (3.01 g) was used as the diazonium precursor. The resulting carbonblack product had a 325 mesh residue of 0.18%, compared to 94% for theuntreated carbon black.

Example 42

Preparation and aqueous dispersibility of a carbon black product

This example shows another preparation of a carbon black product of thepresent invention, and that this carbon black product was more readilydispersible in water than is the correspondingly untreated carbon black.4-Aminophenyl-phosphonic acid (0.90 g) was added to 10 g of ice coldwater. NaOH (0.26 g) was added to dissolve the solid. A cold solution of0.42 g NaNO₂ in 5 g of cold water was added. Concentrated HCl was added(3.83 g) and the solution was stirred at <10° C. for 15 minutes, formingthe corresponding diazonium salt. A cold suspension of 5.02 g of acarbon black with a surface area of 230 m2/g and a DBPA of 70 ml/100 gin 36.2 g of water was added and stirred for 15 minutes. The resultingdispersion was concentrated to dryness under vacuum at room temperaturegiving a carbon black product. This carbon black product dispersesreadily in water, and had a 325 mesh residue of 2.7%, compared to 94%for the untreated carbon black. A sample of the carbon black productthat was dried in an oven at 125° C. did not disperse in water. A sampleof the carbon black product that had been subjected to Soxhletextraction overnight with THF contained 1.57% phosphorous. Therefore,the carbon black product had 0.51 mmol/g of attached p-C₆ H₄ PO₃ ═groups.

Example 43

Preparation and aqueous dispersibility of a carbon black product

This example illustrates the use of a diazonium salt containing aquaternary ammonium salt in the preparation of a carbon black product ofthe present invention and the dispersibility in water of this carbonblack product. A cold solution of 3-amino-N-methyl pyridinium nitrate(11 mmol) in 30 g of water was added to a suspension of 11.0 g of acarbon black (surface area 230, DBPA 70) in 70 g of water at <100° C.Concentrated HCl (2.38 g) was added. A cold solution of 0.92 g NaNO₂ in10 g water was added carefully, and the reaction mixture was stirred for20 minutes. The diazonium salt was formed in situ, and the salt reactedwith the carbon black. A solution of 0.50 g of NaOH in 10 g of water wassubsequently added. The sample was dried at 130° C., giving a carbonblack product. The carbon black product had a 325 mesh residue of 0.40%,compared to 94% for the untreated carbon black product.

Example 44

Preparation and aqueous dispersibility of a carbon black product

This example further illustrates the use of a diazonium salt containinga quaternary ammonium salt in the preparation of a carbon black productof the present invention and the dispersibility in water of this carbonblack product. Using a procedure analogous to that of Example 43 with9.8 mmol 4-(aminophenyl)-trimethylammonium nitrate, 10.0 g carbon black,2.25 g concentrated HCl, 0.83 g NaNO₂, a carbon black product with a325-mesh residue of 0.6% was obtained. The residue of the untreatedcarbon black was 94%.

Example 45

Preparation and aqueous dispersibility of a carbon black product

This example shows that a carbon black product produced with anotherdiazonium salt was more readily dispersible in water than thecorresponding untreated carbon black. The carbon black used fortreatment had a surface area of 230 m2/g and a DBPA of 70 ml/100 g. Acold (5° C.) solution of 4-carboxymethyl-benzenediazonium chloride wasprepared from 0.77 g 4-aminophenylacetic acid, 9.2 g cold water, 1.35 gcold concentrated HCl and 0.44 g NaNO₂. The diazonium solution was addedto an ice cold stirring suspension of 5.04 g of the carbon black in 35.2g of water. Bubbles were released. After stirring for 20 minutes, thedispersion was placed in a water bath at 27° C. and stirred for anadditional 20 minutes. The dispersion was dried in an oven at 120° C.,leaving the carbon black product which had a 325 mesh residue of 2.5%,compared to 94% for the untreated carbon black.

Example 46

Preparation and aqueous dispersibility of a carbon black product

This example shows that a carbon black product with another diazoniumsalt was more readily dispersible in water than the correspondinguntreated carbon black. The carbon black used for treatment has asurface area of 230 m2/g and a DBPA of 70 ml/100 g. A pin pelletizer wascharged with 200 g of the carbon black. A suspension of 80 mmol (12.7 g)sodium 4-aminobenzoate in 45 g of water, 25.7 g concentrated HCl, and asolution of 7.04 g NaNO₂ in 30 g of water were added to the pelletizerin succession, with one minute of mixing after the first two additionsand five minutes after the last. Carboxybenzenediazonium chloride wasformed in situ and it reacted with the carbon black. A solution of 7.83g NaOH in 30 g water was added and mixing was continued for two minutes.The resulting carbon black product was dried at 120° C. and had a 325mesh residue of 6.4%, compared to 94% for the untreated carbon black.

Examples 47-59

Preparation of carbon black products and their use as colorants in ABS

These examples illustrate the preparation of carbon black products ofthe present invention using different amines and the use of these carbonblack products as colorants in ABS. A fluffy carbon black with a surfacearea of 230 m2/g and a DBPA of 70 ml/100 g was used in each example. Adiazonium salt was prepared in an ice bath from the compound indicated,2.2 equivalents of concentrated HCl, and 1.0 equivalents of NaNO₂ as a9.65M solution. The resulting solutions were added to a suspension of200 g of the fluffy carbon black in 3L of water and stirred for 10 to 20minutes. The resulting carbon black product was filtered off, washedwith water twice, and dried at about 100° C. In some instances, thepreparation was carried out by combining multiple batches that had beenmade at one half or. one quarter scale.

Masterbatches were prepared by fluxing 183 g ethylenevinyl acetatepolymer (EVA) for one minute in a Brabender mixer at 110° C., adding45.8 g of the carbon black product, and mixing for four additionalminutes. Injection molded samples for evaluation were prepared byinjection molding a mixture of 80 g of masterbatch and 1520 g of ABS,(acrylonitrile-butadiene-styrene copolymer resin). The finalconcentration of the carbon black product in the molded samples is 1%.

The impact strength of the let down material was measured with an Izodimpact tester; the optical properties were measured with a Huntercalorimeter. The impact strengths obtained are expressed as a percentageof the impact strength of the unfilled ABS used. Desirable propertiesare high impact strength, low Hunter L values (jetter), Hunter a valuesnear 0, and more negative Hunter b values (bluer). Generally when carbonblack is added to ABS to impart color, the impact suffers as the jetnessimproves. The results show that the carbon black products of theinvention are useful as a colorant in ABS.

    ______________________________________                                                       Amount of                                                                              Impact                                                               Diazon-  strength,                                                   Diazon-  ium      % of                                                  Exam- ium      Precursor,                                                                             unfilled                                                                             Hunter                                                                              Hunter                                                                              Hunter                             ple   Precursor                                                                              mmol     ABS    L     a     b                                  ______________________________________                                        47    Aniline  60       84     6.4   -0.2  -1.3                               48    4-Chloro-                                                                              60       87     6.6   -0.3  -1.5                                     aniline                                                                 49    4-Amino- 60       46     6.1   -0.3  -2.0                                     benzoic                                                                       acid                                                                    50    Ethyl 4- 60       71     5.3   -0.3  -1.6                                     amino                                                                         benzoate                                                                51    4-Nitro- 60       58     5.0   -0.3  -1.5                                     aniline                                                                 52    4-Hexyl- 60       73     5.1   -0.3  -1.6                                     aniline                                                                 53    4-       60       66     5.7   -0.3  -1.7                                     Tetra-                                                                        decyl-                                                                        aniline                                                                 54    4-(N,N   60       48     5.7   -0.3  -1.7                                     Dimethyl                                                                      amino)                                                                        aniline                                                                 55    4-Amino  60       54     5.1   -0.3  -1.6                                     aceto-                                                                        phenone                                                                 56    4-Amino  80       50     4.5   -0.2  -1.1                                     phenol                                                                  57    p-       60       45     5.2   -0.3  -1.6                                     Phenylene                                                                     diamine                                                                 58    p-       60       63     5.1   -0.3  -1.6                                     Phene-                                                                        tidine                                                                  59    Reference         53     5.0   -0.2  -1.6                               ______________________________________                                    

Examples 60-62

Preparation of carbon black products and their use as colorants in ABS

These examples illustrate the preparation of carbon black products ofthe present invention using different treating agents and the use ofthose carbon black products as a colorant in ABS. A fluffy carbon blackwith a surface area of 230 m2/g and a DBPA of 70 ml/100 g was used ineach case. The procedure for Examples 47-59 was used for the preparationof the carbon black products using 60 mmol of diazonium precursor.

Masterbatches were prepared by fluxing 203.6 g ABS for two minutes in aBrabender mixer with an initial temperature of 210° C., adding 50.9 g ofthe carbon black product at 175° C., and mixing for three additionalminutes. Injection molded samples for evaluation were prepared byinjection molding a mixture of 75 g of masterbatch and 1425 g of ABS.The final concentration of the carbon black product in the moldedsamples was 1%.

The impact strength of the let down material was measured with an Izodimpact tester; the optical properties were measured with a Huntercalorimeter. The impact strengths obtained are expressed as a percentageof the impact strength of the unfilled ABS used. Desirable propertiesare high impact strength, low Hunter L values (jetter), Hunter a valuesnear 0, and more negative Hunter b values (bluer). Generally when carbonblack is added to ABS to impart color, the impact suffers as the jetnessimproves. The results show that carbon black products of the inventionare useful as a colorant in ABS.

    ______________________________________                                                           Impact                                                                        strength,                                                                     % of                                                               Diazonium  unfilled  Hunter                                                                              Hunter                                                                              Hunter                               Example Precursor  ABS       L     a     b                                    ______________________________________                                        60      4-Aminophenol                                                                            32        4.5   -0.2  -1.1                                 61      p-         37        4.4   -0.1  -1.1                                         Benzonitrile                                                          62      Reference  38        4.6   -0.2  -2.0                                 ______________________________________                                    

Examples 63-65

Preparation of carbon black products and their use in coloringpolyethylene

These examples illustrate the preparation of carbon black products ofthe present invention. A carbon black with a surface area of 140 m2/gand a DBPA of 114 ml/100 g was used. Cold solutions oftetradecylbenzenediazonium chloride were prepared fromtetradecylaniline, concentrated HCl, NaNO2, isopropanol and water. Thediazonium solution was added to 200 g carbon black in a pin pelletizerand mixed for the indicated time. Additional water #1 was added andmixing was continued for three more minutes. After addition of morewater #2 and isopropanol #2 and further mixing, the resulting carbonblack product was dried in an oven. A control sample was prepared bymixing the untreated carbon black in the same pelletizer with water andisopropanol, and drying.

Masterbatches were prepared by mixing 169.34 g low density polyethylenewith 72.6 g of a carbon black sample in a Brabender mixer at 85° C. forfive minutes. Plaques for evaluation were prepared by injection moldinga mixture of 10 g of masterbatch and 1490 g of high densitypolyethylene. The final concentration of carbon black product was 0.2%.The optical properties of the plaques were measured with a Huntercalorimeter. The results show that the carbon black products weresomewhat jetter (lower Hunter L values) than the control and are usefulas a colorant for polyethylene.

    ______________________________________                                                  Example 63                                                                             Example 64 Example 65                                      ______________________________________                                        Precursor   4-         4-         none                                                    Tetradecyl-                                                                              Tetradecyl-                                                        aniline    aniline                                                Precursor amount,                                                                         6.95       11.56      --                                          HCl, g      4.67       7.79       --                                          H2O, g      27         48         --                                          Isopropanol, g                                                                            25         25         --                                          NaNO2, g    2.07       3.45       --                                          Initial mix time,                                                                         3          1          --                                          min                                                                           Added water #1, g                                                                         170        130        --                                          Added water #2, g                                                                         5          5          263                                         Added isopropanol                                                                         --         5          20                                          #2, g                                                                         Final mix time,                                                                           1          2          5                                           min                                                                           Hunter L    6.9        6.7        7.1                                         Hunter a    -0.2       -0.3       -0.3                                        Hunter b    0.3        0.0        0.2                                         ______________________________________                                    

Example 66

Preparation of a carbon black product in a pelletizer

This example illustrates the preparation of a carbon black product ofthe present invention. A pelletizer was charged with 300 g of a carbonblack with a surface area of 254 m2/g and a DBPA of 188 ml/100 g and21.2 g of sulfanilic acid. After mixing for 45 seconds, 220 g of waterwas added. After mixing for 20 seconds, 13.2 g of concentrated nitricacid was added. After mixing for an additional 20 seconds, a solution of10.3 g of NaNO₂ in 270 g of water was added. After mixing for 2 minutes,the resulting carbon black product was dried in an oven at 125° C.

Example 67

Use of a carbon black product in polypropylene

This example illustrates the use of a carbon black product of thepresent invention in polypropylene to impart conductivity to thepolypropylene. A mixture of 263.1 g of the carbon black product ofExample 66 and 881 g of polypropylene was added to a Banbury mixer at66° C. and mixed for 5 minutes. A sample of the material was let down toa 20% carbon black product content on a two roll mill by mixing withadditional polypropylene. The product had a resistivity of 68 ohm-cm,compared to 64 ohm-cm for a similar product made with the untreatedcarbon black used in Example 66.

Examples 68-76

Preparation of carbon black products

These examples show other diazonium compounds that can be used toprepare carbon black products of the present invention. The diazoniumcompounds encompass a range of substitution patterns on the aromaticring and with various electron-withdrawing or electron-donatingsubstituents. In each case, a cold diazonium salt solution was preparedfrom the indicated aryl amine, NaN0₂ and either concentrated HCl orHNO₃. The diazonium solution was added to a suspension of carbon blackin water and/or stirred for 15 to 20 minutes. The resulting carbon blackproduct was isolated by filtration, washed with water, and subjected toSoxhlet extraction with THF overnight. The analyses shown below reportincreases from the reaction over the level contained in the appropriateuntreated carbon black. The results show that a substantial fraction ofthe organic groups are attached to the carbon black product.

    __________________________________________________________________________               Carbon                                                                        black                                                                             Carbon                                                                    product                                                                           black                         Substituted                                 Surface                                                                           product                                                                            Treatment         Fraction of                                                                          phenyl                                      Area                                                                              DBPA Level,                                                                              Cl Analysis                                                                         N Analysis                                                                          bonded groups                                                                        group                            Example                                                                            Aryl amine                                                                          m2/g                                                                              ml/100 g                                                                           μmol/g CB                                                                        μmol/g                                                                           μmol/g                                                                           as %   pmol/g                           __________________________________________________________________________    68   4-Chloro                                                                            230 64   300   196   --    65     196                                   aniline                                                                  69   4-Chloro-3-                                                                         230 64   300   215   --    72     215                                   methyl                                                                        aniline                                                                  70   4-Chloro-2-                                                                         230 64   300   170   --    57     170                                   methyl                                                                        aniline                                                                  71   4-Chloro-3-                                                                         230 64   300   209   --    70     209                                   nitro                                                                         aniline                                                                  72   4-Chloro-2-                                                                         230 64   300   123   --    41     123                                   nitro                                                                         aniline                                                                  73   Sodium 3                                                                            230 64   300   64    --    21     64                                    Amino 6-                                                                      chloro                                                                        benzene                                                                       sulfonate                                                                74   3-Amino                                                                              350*                                                                             120  580   --    461   79     461                                   Pyridine                                                                 75   4-Amino                                                                             230 70   300   --    263   86     263                                   benzoni                                                                       trile                                                                    76   4-Bromo-2-                                                                          230 70   407   264   --    65     264                                   chloro                                                                        aniline                                                                  __________________________________________________________________________     *CTAB Surface area                                                       

Example 77

Preparation of a carbon black product containing aryl and alkoxy groups

This example illustrates the preparation of a carbon black productcontaining aryl and alkoxy groups. A dry sample of a carbon black with asurface area of 230 m2/g and a DBPA of 70 ml/100 g was used.Bromoethanol (30 ml) was added to a mixture of 3 g of the carbon blackand 0.34 g of dry chlorobenzenediazonium hexafluorophosphate. Bubbleswere released rapidly. After stirring for 30 minutes, the resultingcarbon black product was filtered, subjected to Soxhlet extractionovernight with THF and dried. The carbon black product contained 0.58%Cl and 0.84% Br compared to 0.02% Cl and <0.01% Br for the untreatedcarbon black product. The carbon black product therefore had 0.16 mmol/gof attached chlorophenyl groups and 0.11 mmol/g of attached bromoethoxygroups.

Example 78

Preparation of a carbon black product containing aryl and alkoxy groups

This example illustrates the preparation of a carbon black productcontaining aryl and alkoxy groups. A dry sample of a carbon black with asurface area of 230 m2/g and a DBPA of 70 ml/100 g was used.Chloroethanol (30 ml) was added to a mixture of 3 g of the carbon blackand 0.32 g of dry bromobenzenediazonium tetrafluoroborate. Bubbles werereleased rapidly. After stirring for 30 minutes, the resulting carbonblack product was filtered, subjected to Soxhlet extraction overnightwith THF and dried. The carbon black product contained 0.31% Cl and1.60% Br compared to 0.02% Cl and 0.01% Br for the untreated carbonblack. The carbon black product therefore had 0.20 mmol/g of attachedbromophenyl groups and 0.08 mmol/g of attached chloroethoxy groups.

Example 79

Preparation of a carbon black product containing aryl and alkoxy groups

This example illustrates another method for the preparation of a carbonblack product containing aryl and alkoxy groups. A carbon black with asurface area of 230 m2/g and a DBPA of 70 ml/100 g was used. A solutionof 4-bromobenzene diazonium nitrate was prepared in an ice bath from0.69 g bromoaniline, 0.33 g NaNO₂, 0.86 g concentrated HNO3 and ca. 3 mlof water. The diazonium solution was added to a suspension of 10 gcarbon black product, 5 g chloroethanol and 85 g water that was stirringat room temperature. After stirring for 30 minutes, the carbon blackproduct was removed by filtration, washed with THF, and dried in an ovenat about 125° C. A sample that had been subjected to Soxhlet extractionovernight with THF contained 1.08% bromine and 0.16% chlorine. A controlcarbon black sample was prepared by stirring the same untreated carbonblack in a 5.6% chloroethanol/water solution, washing with THF, dryingand extracting with THF. The control contained 0.02% bromine and 0.082%chlorine. The carbon black product therefore had 0.13 mmol/g of attachedbromophenyl groups and 0.022 mmol/g of attached chloroethoxy groups.

Example 80

Preparation of a carbon black product

This example further illustrates the preparation of a carbon blackproduct of the present invention. Concentrated HCl (16.2 g) was dilutedwith 40 g water and added to 9.30 g 4-aminophenyldisulfide. The mixturewas stirred in an ice bath. A cold solution of 6.21 g NaNO₂ in 30 gwater was added with stirring, keeping the mixture below 10° C.4-Diazophenyl disulfide dichloride is formed. The mixture was added to asuspension of 250 g of pelleted carbon black (iodine number of 120 mg/gand a DBPA of 125 ml/100 g) in 1.3L of water at 10° C. with stirring.Bubbles were released. After stirring for 2 1/2 hours, the product isfiltered, washed with ethanol, washed with additional water and thendried at 125° C. to a constant weight. A sample of the carbon blackproduct that was extracted overnight with THF and dried contained 1.75%sulfur, compared to 1.08% for the untreated carbon black. Therefore, thecarbon black product had 0.10 mmol/g of attached dithiodi-4,1-phenylenegroups.

Example 81

Preparation of a carbon black product

This example illustrates the preparation of a carbon black product ofthe present invention. Concentrated HCl (5.4 g) was diluted with 40 gwater and added to 3.1 g 4-aminophenyldisulfide. The mixture was stirredin an ice bath, and 50 g additional cold water was added. A coldsolution of 2.07 g NaNO₂ in 30 g water was added with stirring, keepingthe mixture below 10° C. 4-Diazophenyl disulfide dichloride was formed.The mixture was added to a suspension of 125 g of pelleted carbon black(iodine number of 120 mg/g and a DBPA of 125 ml/100 g) in about 800 g ofwater at 10°-15° C. with stirring. Bubbles were released. After stirringfor 2 hours, the resulting carbon black product was filtered, washedwith ethanol, washed with additional water and then dried at 125° C. toa constant weight. A sample of the carbon black product that wasextracted overnight with THF and dried contained 1.56% sulfur, comparedto 1.08% for the untreated carbon black. Therefore, the carbon blackproduct had 0.075 mmol/g of attached dithiodi-4,1-phenylene groups.

Example 82

Preparation of a carbon black product

This example further illustrates the preparation of a carbon blackproduct of the present invention. A pelleted carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 ml/100 g was used. Butyl lithium(50 mL of a 1.0M solution in hexane) was added to 200 mL of dry DMSOunder nitrogen. A solution of 11.1 g of 4-aminophenyl disulfide in 100mL dry DMSO was prepared and added under nitrogen with cooling from anice bath. A dark violet colored developed. S₂ C₁₂ (3.3 mL) was addedover 10 minutes with stirring and continued cooling. A solution of 1.7 gNaOH in water was added. After addition of more water, the product wasextracted with 450 mL of ether. The ether was removed under vacuum, andthe residue was dissolved in CH₂ C₁₂, washed with water, dried andconcentrated under vacuum to give 4-aminophenyltetrasulfide as an oil.

4-Aminophenyl tetrasulfide (5.85 g) was stirred with 150 g of water inan ice bath. A cold solution of 8.1 g concentrated HCl in 50 g water wasadded, followed gradually by a solution of 3.2 g NaNO₂ in 40 g water,forming 4-diazophenyl tetrasulfide dichloride. After stirring, theresulting suspension was added to a stirring slurry of 125 g of thepelleted carbon black in about 800 g of water. Bubbles were released.After stirring for 2 1/2 hours, the resulting carbon black product wasfiltered off, washed with ethanol, washed with water and dried at 140°C. A sample of the carbon black product that had been extracted with THFovernight and dried contained 1.97% sulfur, compared to 1.08% for theuntreated black. Therefore, the carbon black product had 0.07 mmol/g ofattached tetrathiodi-4,1-phenylene groups.

Example 83

Preparation of a carbon black product

This example illustrates the preparation of a carbon black product ofthe present invention. A carbon black with an iodine number of 120 mg/gand a DBPA of 125 ml/100 g was used. A cold solution of 2.65 gconcentrated HCl and 30 g water was added to a mixture of 2.85 g4-aminophenyl phenyl disulfide in 50 g water that was stirring in an icebath. A cold solution of 1.04 g NaNO₂ in 30 g of water was added over aperiod of 10 minutes. 4-Diazophenyl phenyl. disulfide chloride wasformed. The diazonium suspension was added to a suspension of 122 gcarbon black in about 800 g water that was stirring at 15° C. Bubbleswere released. After stirring for about two hours, the carbon blackproduct was filtered off, washed with isopropanol, washed with water,and dried in an oven at about 125° C. A sample of the carbon blackproduct that had been subjected to Soxhlet extraction overnight with THFand dried had a-sulfur content of 1.32%, compared to 1.08% for theuntreated carbon black. Therefore, the carbon black product had 0.038mmol/g of attached phenyldithiophenylene groups.

Example 84

Preparation of a carbon black product

This example further illustrates the preparation of a carbon blackproduct of the present invention. Nitrogen dioxide (4.1 g) was bubbledinto 40 g water that was cooled in an ice bath. The resulting solutionwas added slowly to a cold (10° C.), stirring suspension of 4.65 g of4-aminophenyl disulfide in 100 g water. The resulting solution of4-diazophenyl disulfide dinitrate was added to a cold stirringsuspension of 125 g of carbon black (iodine number of 120 mg/g and aDBPA of 125 ml/100 g) in 800 g cold (12°-14° C.) water. The reactionmixture was stirred for 3 days, and allowed to warm to room temperaturein the process. The resulting carbon black product was recovered byfiltration and was dried. A sample of the carbon black product extractedwith THF overnight had 1.81% sulfur, compared to 1.07% sulfur in theuntreated carbon black product. Therefore, the carbon black product had0.12 mmol/g of attached dithiodi-4,1-phenylene groups.

Example 85

Preparation of a carbon black product

This example further illustrates the preparation of a carbon blackproduct of the present invention. The procedure of Example 80 wasfollowed, except that a carbon black with an iodine number of 90 mg/gand a DBPA of 114 ml/100 g was used, and except that an additional 50 mlof water was used to form the aminophenyl disulfide dihydrochloridesuspension. A sample of the resulting carbon black product that had beenextracted overnight with THF and dried contained 2.12% sulfur, comparedto 1.45% for the untreated carbon black. Therefore, the carbon blackproduct had 0.10 mmol/g of attached dithiodi-4,1-phenylene groups.

Example 86

Preparation of a carbon black product

This example illustrates the preparation of a carbon black product ofthe present invention. A carbon black with an iodine number of 120 mg/gand a DBPA of 125 ml/100 g was used. A cold solution of4-diazo-2-chlorophenyl disulfide dichloride was prepared by adding acold solution of 3.59 g of NaNO₂ in 40 g water to a suspension of 6.6 g4-amino-2-chlorophenyl disulfide, 9.12 g concentrated HCl and about 150g water that was stirring in an ice bath. After stirring for fiveminutes, the diazonium solution was then added to a stirred suspensionof 140 g of carbon black in 1 liter of water at 10°-14° C. Afterstirring for two hours, the resulting carbon black product was filteredoff, washed with ethanol, washed with water, and then dried in an ovenat 125° C. A sample of the carbon black product that was subjected toSoxhlet extraction overnight with THF and dried had a sulfur content of1.60%, compared to 1.08% for the untreated carbon black. Therefore, thecarbon black product had 0.081 mmol/g of attacheddithiodi-4,1-(3-chlorophenylene) groups.

Example 87

Preparation of a carbon black product with a diazonium salt generated insitu

This example illustrates the preparation of a carbon black product ofthe present invention with a diazonium salt that is generated in situ. Acarbon black with an iodine number of 120 mg/g and a DBPA of 125 ml/100g was used. 4-Aminophenyl disulfide (8.38 g) was dissolved in a solutionof 14.65 g of concentrated HCl and about 150 g of water, and added to astirred slurry of 225 g of carbon black in about 1.4 L of water. Asolution of 5.28 g NaNO₂ in about 50 g water was added, forming4-diazophenyl disulfide in situ, which reacted with the carbon black.After stirring for two hours, the resulting carbon black product wasremoved by filtration, washed with ethanol, washed with water, and driedat about 125° C. A sample of the carbon black product that had beensubjected to Soxhlet extraction overnight with THF and dried contained1.89% sulfur, compared against 1.08% for the untreated carbon black.Therefore, the carbon black product had 0.13 mmol/g of attacheddithiodi-4,1-phenylene groups.

Example 88

Preparation of a carbon black product

A carbon black product having attached dithiodi-4,1-phenylene groups wasprepared by following the method of Example 80 and using a suspension of8.38 g 4-aminophenyl disulfide in about 100 g of water, a solution of13.65 g concentrated HCl in 40 g of water, a solution of 5.04 g NaNO₂ in30 g of water, and a slurry of 225 g of the same carbon black in 1.4 Lof water. The carbon black slurry was stirred at 10°-14° C. when thediazonium solution was added.

Examples 89 and 90

Comparative carbon black products

In these comparative examples, the carbon blacks used in Examples 80 and85 were washed with water, ethanol and water, and subsequently dried togive the comparative carbon black products of Examples 88 and 89,respectively.

Examples 91-99

Use of different carbon blacks for the preparation of carbon blackproducts that are water dispersible

This example shows the use of a variety of carbon blacks in thepreparation of carbon black products of the present invention. Thisexample also shows that the carbon black products were more readilydispersible in water than the corresponding unreacted carbon blacks.Sulfanilic acid was dissolved in 200 g of hot water. The carbon blackproduct (30 g) was added and the mixture was allowed to cool to 25° to30° C. Concentrated HCl was added (2.15 equivalents based on thesulfanilic acid used) and then a 9.65M solution of NaNO₂ in water wasadded (1.2 equivalents based on the sulfanilic acid used), forming4-sulfobenzenediazonium hydroxide in situ, which reacted with the carbonblack. After stirring for 30 minutes, the resulting dispersion was driedin an oven at 100° C., giving the resulting carbon black product.

    ______________________________________                                              Original Original                Residue of                                   Carbon   Carbon          Residue of                                                                            untreated                                    Black    black           a carbon                                                                              carbon                                 Ex-   Surface  product  Sulfanilic                                                                           black   black                                  ample Area m2/g                                                                              ml/100 g acid g product, %                                                                            product, %                             ______________________________________                                        91    350**    120      6.98   1.0     97                                     92    140      114      3.03   0.6*    45                                     93    1500     330      32.55  0.6*    35                                     94    42       121      0.91   0.1     26                                     95    80        85      1.73   <0.1    81                                     96    24       132      0.44   4.6     31                                     97    24       132      1.50   0.2     31                                     98    254      178      5.43   <0.1    23                                     99    18        39      0.93   4.4     40                                     ______________________________________                                         *Filtered through a 20 micron filter.                                         **CTAB surface area                                                      

Example 100

Preparation of a carbon black product and its use in the preparation ofblack paper

This example shows the preparation of a carbon black product of thepresent invention and the use of that product in the preparation ofblack paper. A carbon black (300 g) with a surface area of 80 m2/g and aDBPA of 85 ml/100 g was added to a pin pelletizer with 18.2 g ofsulfanilic acid. After mixing briefly, 150 g of water, 11.2 g ofconcentrated nitric acid, 30 g of water and a solution of 8.78 g ofNaNO2 in 35 g of water were added in succession with 15 seconds ofmixing after each addition. 4-Sulfobenzenediazonium hydroxide inner saltwas formed in situ and it reacted with the carbon black. The resultingcarbon black product was dried in an oven at 125° C. A dispersion ofthis carbon black product was prepared by dispersing it in water in alaboratory homogenizer for 30 seconds.

A comparative dispersion was made by grinding 200 g of the sameunreacted carbon black in a solution of 7 g of a lignosulfonatedipsersant, 5 ml concentrated NH₄ OH and 770 g water with grinding mediain a ball mill for 4 hours, at which point a Hegman gauge reading of 7was obtained. Penobscott bleached hardwood kraft pulp (160 g) and St.Felician bleached softwood kraft pulp (240 g) were dispersed in water ina Cowles dissolver. The stock solution was transferred into a TAPPIstandard laboratory beater and diluted to a volume of 23 liters. Thestock solution was circulated in the beater for five minutes, and thenplaced under load and beaten for 50 minutes to a corrected CanadianStandard Freeness of 355 ml.

Sufficient pulp to make three 2.75 g hand sheets was diluted to 3 L, andthe appropriate amount of carbon black dispersion was incorporated. Asuspension was prepared for each carbon black loading level. Eachsuspension was divided into three portions. The first portion was usedas is. Rosin and alum were added to the second portion at the rates of80 pounds and 60 pounds per bone dry ton, respectively. HERCON 79 (AKD)size and BL 535 retention aid were added to the third portion at therates of four pounds and three pounds per bone dry ton, respectively.One 8"×8" Noble & Wood handsheet was made from each sample. Theresulting handsheets were evaluated for TAPPI brightness using 45°/0°geometry.

HERCON is a registered trademark for sizes produced and sold by HerculesInc., Wilmington Del. BL 535 is available from Buckman Laboratories,Inc., Memphis Tenn.

The following table shows the brightness of handsheets made with thecarbon black product dispersion and with the control dispersion. Thesedata show that the carbon black product can be used to color paper.These data also show that when the paper was made with an acidic rosinsize and an alum retention aid, the carbon black product was retainedmore efficiently and advantageously at low loading levels when comparedagainst the unreacted carbon black. These data further show that whenthe paper was made with an alkaline AKD size and BL 535 retention aid,the carbon black product was retained more efficiently andadvantageously at low loading levels when compared against the unreactedcarbon black.

    ______________________________________                                        Carbon                                                                        black                                Brightness,                              product,                   Brightness,                                                                             Untreated                                pounds                     Treated carbon                                                                          carbon black                             per bone                   black product                                                                           product                                  dry ton None   AKD    Alum Side A                                                                              Side B                                                                              Side A                                                                              Side B                           ______________________________________                                        10      X                  61    69    46    50                               15      X                  61    61    43    50                               25      X                  59    61    34    41                               50      X                  44    41    18    24                               100            X           33    36     9    13                               200            X           20    23     0     5                               10             X           16    18    21    23                               15             X           12    13    19    21                               25             X           11    13    14    16                               50             X            7     8    10    11                               100            X            7     1     1     8                               200            X            4     5     5     5                               10                    X    16    20    22    24                               15                    X    13    16    19    21                               25                    X    11    12    13    14                               50                    X     8    10     9    11                               100                   X     7     9     6     7                               200                   X     6     8     4     5                               ______________________________________                                    

Example 101

Use of a carbon black product in the preparation of an aqueous ink

This example illustrates the advantages of using a carbon black productof the present invention in an aqueous ink formulation. Ink compositionA was prepared by adding 3.13 parts of the carbon black product ofExample 13 to a vehicle made by mixing 2.92 parts JONCRYL 61LV resin,0.21 parts isopropanol, 0.31 parts ARROWFLEX defoamer, 7.29 partsJONCRYL 89 resin and 6.98 parts water, and shaking the composition for10 minutes on a paint shaker. The table below shows the 635 mesh residuelevel.

JONCRYL is a registered trademark for resins produced and sold by SCJohnson Polymer, Racine, Wis. ARROWFLEX is a registered trademark fordefoamers produced and sold by Witco, New York, N.Y.

Ink composition B was prepared by grinding a mixture of 120 parts of thecarbon black product used in Example 13, 112 parts of JONCRYL 61LVresin, 8 parts of isopropanol, 4 parts of ARROWFLEX defoamer, 156 partsof water and 400 g of grinding media. In order to check the grind level,samples were periodically let down to composition C that contained 15.0parts carbon black product, 14.0 parts JONCRYL 61LV resin, 1.0 partsisopropanol, 1.7 parts ARROWFLEX DEFOAMER, 35.1 parts Joncryl 89 and33.4 parts water.

Ink composition D was prepared by grinding a mixture of 120 parts of theuntreated carbon black used in Example 13, 112 parts of JONCRYL 61LVresin, 8 parts of isopropanol, 4 parts of ARROWFELX defoamer, 156 partsof water and 400 g of grinding media. In order to check the grind level,samples were periodically let down to composition E that contained 15.0parts carbon black product, 14.0 parts JONCRYL 61LV resin, 1.0 partsisopropanol, 1.7 parts ARROWFLEX defoamer, 35.1 parts JONCRYL 89 resinand 33.4 parts water.

The residues from ink compositions A, C and E as a function of grindingtime are provided in the following table, and clearly show that a carbonblack product of the present invention disperses more readily than thecorresponding unreacted carbon black in these aqueous inks.

    ______________________________________                                                     Ink A      Ink C      Ink E                                                   635 Mesh   635 Mesh   635 Mesh                                   Dispersion time                                                                            Residue, % Residue, % Residue, %                                 ______________________________________                                        10 Minutes shaking                                                                         2.6        --         --                                         20 Minutes Ball Mill                                                                       --         0.3        --                                         40 Minutes Ball Mill                                                                       --         0.2        --                                          1 Hour Ball Mill                                                                          --         0.02       about                                                                              100                                    2 Hours Ball Mill                                                                         --         --               10.8                                  3 Hours Ball Mill                                                                         --         --               5.8                                   4 Hours Ball Mill                                                                         --         --               0.9                                  10 Hours Ball Mill                                                                         --         --               0.5                                  14 Hours Ball Mill                                                                         --         --               0.3                                  15 Hours Ball Mill                                                                         --         --               1.0                                  16 Hours Ball Mill                                                                         --         --               1.0                                  ______________________________________                                    

Example 102

Use of a carbon black product in the preparation of an aqueous coating

This example shows that carbon black products of the present inventionare useful for the preparation of aqueous coatings. The carbon blackproduct from Example 9 (10 g) was dispersed in 90 g of water by stirringfor 10 minutes. Coating composition A was prepared by stirring 4.3 g ofthis dispersion into a mixture of 7.53 g of CARGILL 17-7240 acrylicresin, 0.80 g of dimethylethanolamine (DMEA), 19.57 g water, 0.37 gSURFYNOL CT136 surfactant, 1.32 g CARGILL 23-2347 melamine resin, 0.53 gethylene glycol monobutyl ether and 0.075 g BYK-306 surfactant. CARGILL17-7240 acrylic resin and CARGILL 23-2347 melamine resin are availablefrom Cargill Inc., Minneapolis, Minn. SURFYNOL CT136 is a registeredtrademark for surfactants produced and sold by Air Products andChemicals, Inc., Allentown, Pa. BYK-306 is a registered trademark forsurfactants produced and sold by BYK-Chemie USA, Wallingford.

A millbase was prepared by grinding an oxidized carbon black product (15g) with a surface area of 560 m2/g, a DBPA of 80 ml/100 g and a volatilecontent of 9% in a mixture of 74.6 g of CARGILL 17-7240 acrylic.resin,9.53 g DMEA, 236.5 g water and 16.35 g CT-136 surfactant until its meanvolume particle size was 0.18 microns. Comparative coating composition Bwas prepared by mixing 24.4 g of this millbase with a mixture of 17.51 gCARGILL 17-7240 acrylic resin, 1.74 g DMEA, 50.56 g water, 3.97 gCARGILL 23-2347 melamine resin, 1.59 g ethylene glycol monobutyl etherand 0.23 g BYK-306 surfactant.

Glossy lenetta paper coated with compositions A and B was dried at 350°F. for 10 minutes. A clear coat was applied, and the samples were driedagain. The paper coated with composition A had Hunter L,a,b values of1.0, 0.01 and 0.03, respectively, compared to 1.1, 0.01 and -0.06,respectively for the paper coated with comparative composition B.

Example 103

Preparation of a carbon black product and its use in an aqueous coating

This example illustrates the preparation of a carbon black product ofthe present invention and the use of this carbon black product in anaqueous coating. A carbon black (200 g) with a CTAB surface area of 350m2/g and a DBPA of 120 ml/100 g was added to a stirred solution of 42.4g sulfanilic acid in 2800 g of water. Nitrogen dioxide (25.5 g) wasdissolved in 100 g of cold water and added to the carbon black productsuspension. Bubbles were released. 4-Sulfobenzenediazonium hydroxideinner salt was formed in situ, which reacted with the carbon black.After stirring for one hour, 5 g of additional NO₂ was added directly tothe carbon black dispersion. The dispersion was stirred for anadditional 15 minutes, and left overnight. The resulting carbon blackproduct was recovered by drying the dispersion in an oven at 130° C.

A dispersion of this carbon black product was prepared by stirring 10 gof the carbon black product in 90 g of water. Coating composition C wasprepared by stirring 4.3 g of this dispersion into a mixture of 7.53 gof CARGILL 17-7240 acrylic resin, 0.80 g of DMEA, 19.57 g water, 0.37 gSURFYNOL CT136 surfactant, 1.32 g CARGILL 23-2347 melamine resin, 0.53 gethylene glycol monobutyl ether and 0.075 g BYK-306 surfactant.

A millbase was prepared by grinding (in an attritor) an oxidized carbonblack product (15 g) with a surface area of 560 m2/g, a DBPA of 91ml/100 g and a volatile content of 9.5% in a mixture of 74.6 g ofCARGILL 17-7240 acrylic resin, 9.53 g DMEA, 236.5 g water and 16.35 gSURFYNOL CT-136 surfactant for 24 hours. Comparative coating compositionD was prepared by mixing 24.4 g of this millbase with a mixture of 17.51g CARGILL 17-7240 acrylic resin, 1.74 g DMEA, 50.56 g water, 3.97 gCARGILL 23-2347 melamine resin, 1.59 g ethylene glycol monobutyl etherand 0.23 g BYK-306 surfactant.

Glossy lenetta paper coated with compositions A and B was dried at 350°F. for 10 minutes. A clear coat was applied, and the samples were driedagain. The paper coated with composition C had Hunter L, a, and b valuesof 1.0, 0.01 and 0.03, respectively, compared to 1.1, 0.01 and -0.06,respectively for the paper coated with comparative composition D.

Examples 104-108

Use of carbon black products in rubber formulations

This example illustrates the use of the carbon black products ofexamples 80 to 84 and the comparative example 89 in rubber formulations.The polymer is milled in a Brabender mixer for 1 minute at 100° C. Amixture of ZnO and the carbon black product was added and mixed for 2additional minutes. The stearic acid and FLEXZONE 7P anti-degradant wereadded and mixed for 2 additional minutes. The sample was dumped, cooledand mixed at 80° C. for 1 minute, the curatives were added, and themixing was continued for an additional minute. The sample was thenpassed through a two roll mill three times. The recipes and performancedata in each case are given in the tables below. NS 114 is a chemicallymodified tin coupled solution SBR available from Nippon Zeon, Japan.FLEXZONE is a registered trademark for antidegradant products availablefrom Uniroyal Chemical, Naugatuck, Conn.

    ______________________________________                                        Example    104    105    106  107  108  Comparative                           ______________________________________                                        NS 114     100    100    100  100  100  100                                   CB Product 50                                                                 Example 80                                                                    CB Product        50                                                          Example 81                                                                    CB Product               50                                                   Example 82                                                                    CB Product                    50                                              Example 83                                                                    CB Product                         50                                         Example 84                                                                    Control CB                              50                                    Example 89                                                                    ZnO        3      3      3    3    3    3                                     Stearic Acid                                                                             2      2      2    2    2    2                                     FLEXZONE 7P                                                                              1      1      1    1    1    1                                     product                                                                       CBS *      1.25   1.25   1.25 1.25 1.25 1.25                                  MBT **     0.2    0.2    0.2  0.2  0.2  0.2                                   Sulfur     1.75   1.75   1.75 1.75 1.75 1.75                                  Total      159.2  159.2  159.2                                                                              159.2                                                                              159.2                                                                              159.2                                 ______________________________________                                         * CBS = cyclohexylbenzothiazylsulfenamide                                     ** MBT = mercaptobenzothiazole                                           

    __________________________________________________________________________                                            Abrader                                                                           Abrader                           100%       300%              Bound      index                                                                             index                             Modulus    Modulus                                                                            Tensile                                                                           Elong.                                                                            Hardness                                                                           rubber                                                                            Tan δ                                                                      Tan δ                                                                       14% 21%                               Mpa        Mpa  Mpa %   Shore A                                                                            %   0° C.                                                                     70° C.                                                                     slip                                                                              slip                              __________________________________________________________________________    Example 104                                                                         4.18 --   19.5                                                                              290 60   44.5                                                                              0.244                                                                            0.114                                                                             122 142                               Example 105                                                                         3.93 --   16.7                                                                              274 60   39.6                                                                              0.265                                                                            0.137                                                                             114 141                               Example 106                                                                         4.33 19.1 20.9                                                                              314 61   35.2                                                                              0.277                                                                            0.131                                                                             110 132                               Example 107                                                                         3.44 15.2 19.6                                                                              372 61   30.8                                                                              0.304                                                                            0.170                                                                             103 105                               Example 108                                                                         3.67 17.6 19.6                                                                              335 60   40.9                                                                              0.251                                                                            0.122                                                                             113 129                               Comparative                                                                         3.25 14.1 18.4                                                                              385 60   28.1                                                                              0.327                                                                            0.173                                                                             100 100                               __________________________________________________________________________

These data show that carbon black products of the present invention areuseful in rubber formulations. They further show that significantincreases in modulus, bound rubber and abrasion resistance are obtained,as are significant decreases in Tan δ. The magnitude of the effectdepends on the treatment level as well as on the specific group attachedto the carbon black product.

Examples 109-112

Use of a carbon black product in rubber formulations

This example illustrates the use of a carbon black product of thepresent invention in several different rubber formulations. Rubbercompounds were prepared from the carbon black product of Example 85 andof the comparative carbon black product of Example 90 by the methoddescribed for examples 104-108 using the recipes below. DURADENE 715 isa solution SBR. DURADENE is a registered trademark for SBR productsavailable from Firestone, Akron Ohio.

    __________________________________________________________________________    Example                                                                              109 Comparative                                                                         110 Comparative                                                                         111 Comparative                                                                         112 Comparative                          __________________________________________________________________________    SBR    100 100                                                                1500                                                                          Duradene 715     100 100             50  50                                   NR                         100 100   50  50                                   CB Product                                                                           50        50        50        50                                       Example                                                                       85                                                                            Control    50        50        50        50                                   CB                                                                            Example                                                                       90                                                                            ZnO    3   3     3   3     4   4     3   3                                    Stearic                                                                              2   2     2   2     2   2     2   2                                    Acid                                                                          Flexzone                                                                             1   1     1   1     1   1     1   1                                    7P                                                                            CBS    1.25                                                                              1.25  1.25                                                                              1     1   1     1.25                                                                              1.25                                 MBT    0.2 0.2   0.2 0.2                                                      Sulfur 1.75                                                                              1.75  1.75                                                                              1.75  1.5 1.5   1.5 1.5                                  Total  159.2                                                                             159.2 159.2                                                                             159.2 159.5                                                                             159.5 158.75                                                                            158.75                               __________________________________________________________________________

The performance data in the table below show that carbon black productsaccording to the invention are useful in several different rubberformulations.

    __________________________________________________________________________                                             Abrader                                                                           Abrader                          100%       300%              Bound       index                                                                             index                            Modulus    Modulus                                                                            Tensile                                                                           Elong.                                                                            Hardness                                                                           rubber                                                                            Tan Tan 14% 21%                              Mpa        Mpa  Mpa %   Shore A                                                                            %   δ 0 C.                                                                      δ 70 C.                                                                     slip                                                                              slip                             __________________________________________________________________________    Example 109                                                                         4.12 19.3 21.9                                                                              338 60   29.8                                                                              0.241                                                                             0.155                                                                              84 117                              Comparative                                                                         3.70 17.3 23.0                                                                              393 62   28.0                                                                              0.280                                                                             0.182                                                                             100 100                              Example 110                                                                         4.79 --   14.4                                                                              233 63   32.4                                                                              0.477                                                                             0.146                                                                              81 175                              Comparative                                                                         4.10 --   16.3                                                                              282 61   28.6                                                                              o.544                                                                             0.173                                                                             100 100                              Example 111                                                                         3.32 15.1 24.4                                                                              456 55   39.1                                                                              0.221                                                                             0.142                                                                              98 135                              Comparative                                                                         3.48 17.1 27.3                                                                              468 57   43.6                                                                              0.240                                                                             0.138                                                                             100 100                              Example 112                                                                         3.77 15.7 19.0                                                                              358 58   33.3                                                                              0.296                                                                             0.156                                                                             100 176                              Comparative                                                                         3.39 15.4 23.3                                                                              441 58   35.i                                                                              0.335                                                                             0.175                                                                             100 100                              __________________________________________________________________________

Example 113

Use of treated carbon black in a rubber formulation

This example illustrates the use of a treated carbon black of thepresent invention in a rubber formulation. Rubber compounds wereprepared from the treated carbon black of example 86 and the comparativecarbon black of example 89 by the method described in examples 104-108.The formulations and performance data are shown in the following tables.These results show that the treated carbon black is useful in thisrubber formulation. NS 116 is a chemically modified tin coupled solutionSBR and is available from Nippon Zeon, Japan.

    ______________________________________                                        Example          113    Comparative                                           ______________________________________                                        NS 116           100    100                                                   CB Product       50                                                           Example 86                                                                    Control CB              50                                                    Example 89                                                                    ZnO              3      3                                                     Stearic Acid     2      2                                                     FLEXZONE 7P      1      1                                                     product                                                                       CBS              1.25   1.25                                                  MBT              0.2    0.2                                                   Sulfur           1.75   1.75                                                  Total            159.2  159.2                                                 ______________________________________                                    

    __________________________________________________________________________                                             Abrader                                                                           Abrader                          100%       300%              Bound       index                                                                             index                            Modulus    Modulus                                                                            Tensile                                                                           Elong.                                                                            Hardness                                                                           rubber                                                                            Tan Tan 14% 21%                              Mpa        Mpa  Mpa %   Shore A                                                                            %   δ 0 C.                                                                      δ 70 C.                                                                     slip                                                                              slip                             __________________________________________________________________________    Example                                                                             4.46 17.3 18.3                                                                              316 64   28.0                                                                              0.787                                                                             0.190                                                                             72  110                              113                                                                           Comparative                                                                         4.12 16.7 21.2                                                                              367 63   26.2                                                                              0.818                                                                             0.219                                                                             100 100                              __________________________________________________________________________

Example 114

Use of a carbon black product in a rubber formulation

This example illustrates the use of a carbon black product of thepresent invention in a rubber formulation. Rubber compounds wereprepared from the carbon black product of Example 87 and the comparativecarbon black of Example 89 by the method described in Examples 104-108.The formulations and performance data are shown in the following tables.These results show that the carbon black product is useful in thisrubber formulation.

    ______________________________________                                        Example          114    Comparative                                           ______________________________________                                        NS 116           100    100                                                   CB Product       50                                                           Example 87                                                                    Control CB              50                                                    Example 89                                                                    ZnO              3      3                                                     Stearic Acid     2      2                                                     FLEXZONE 7P      1      1                                                     product                                                                       CBS              1.25   1.25                                                  MBT              0.2    0.2                                                   Sulfur           1.75   1.75                                                  Total            159.2  159.2                                                 ______________________________________                                    

    __________________________________________________________________________                                             Abrader                                                                           Abrader                          100%       300%                          index                                                                             index                            Modulus    Modulus                                                                            Tensile                                                                           Elong.                                                                            Hardness                                                                           Bound                                                                              Tan δ                                                                      Tan δ                                                                       14% 21%                              Mpa        Mpa  Mpa %   Shore A                                                                            rubber %                                                                           0° C.                                                                     70° C.                                                                     slip                                                                              slip                             __________________________________________________________________________    Example                                                                             5.04 --   16.6                                                                              242 60   39.0 0.816                                                                            0.145                                                                             88  137                              114                                                                           Comparative                                                                         4.12 16.7 21.2                                                                              367 63   26.2 0.818                                                                            0.219                                                                             100 100                              __________________________________________________________________________

Examples 115-116

Use of carbon black product in rubber formulations

These examples illustrate the use of a carbon black product of thepresent invention in two rubber formulations that are peroxide cured.Rubber compounds were prepared from the carbon black product of Example88 and from an untreated comparative carbon black with an iodine numberof 120 mg/g and a DBPA of 125 ml/100 g. The method described in Examples104-108 was used with the recipies below.

    ______________________________________                                        Example    115    Comparative 116  Comparative                                ______________________________________                                        NS-114     100    100                                                         Duradene                      100  100                                        715                                                                           CB         50                 50                                              Product                                                                       Example 88                                                                    Control CB        50               50                                         ZnO        3      3           3    3                                          Stearic    2      2           2    2                                          Acid                                                                          Flexzone   1      1           1    1                                          7P                                                                            Dicumyl    2      2           2    2                                          peroxide                                                                      Total      158    158         158  158                                        ______________________________________                                    

These performance data in the table below show that this carbon blackproduct is useful in rubber formulations using peroxide cure.

    __________________________________________________________________________                                            Abrader                                                                           Abrader                           100%       300%              Bound      index                                                                             index                             Modulus    Modulus                                                                            Tensile                                                                           Elong.                                                                            Hardness                                                                           rubber                                                                            Tan                                                                              Tan δ                                                                       14% 21%                               Mpa        Mpa  Mpa %   Shore A                                                                            %   δ °C.                                                               70° C.                                                                     slip                                                                              slip                              __________________________________________________________________________    Example 115                                                                         3.66 10.4 23.9                                                                              356 61   3.3 0.208                                                                            0.119                                                                              96 101                               Comparative                                                                         2.94  8.1 21.8                                                                              398 62   18  0.284                                                                            0.156                                                                             100 100                               Example 116                                                                         5.11 11.5 13.9                                                                              233 67   17.5                                                                              0.299                                                                            0.152                                                                              65  74                               Comparative                                                                         4.07 11.3 20.3                                                                              321 61   22.1                                                                              0.343                                                                            0.180                                                                             100 100                               __________________________________________________________________________

Example 117

Use of a carbon black product to color textiles

This example illustrates the use of a carbon black of the presentinvention to color textiles. Samples of textiles were placed for thetime indicated below in a stirring dispersion of the carbon blackproduct of Example 16 having attached C₆ H₄ SO₃ -- groups at theindicated concentrations at 100° C. The pH was adjusted as shown. Thesamples were removed, allowed to drain briefly, and posttreated byplacing for about 30 seconds in hot water, a hot 1M solution of NaCl ora hot 0.015M solution of Al₂ (SO₄)₃. When the pH of the carbondispersion was adjusted, the pH of the NaCl and Al₂ (SO₄)₃ posttreatmentsolutions were adjusted to match. The samples were then washed withwater and dried. The L values below show that the textiles wereeffectively colored with the carbon black product. Lower L valuesrepresent darker materials.

    ______________________________________                                        Carbon                                                                        conc.            Time   Post treatment                                        Textile                                                                              M       pH    Min. H2O  NaCl Al2 (SO4)3                                                                            Hunter L                          ______________________________________                                        Cotton 0.1     A     15             X       34.1                              Cotton 0.1     A     45   X                 33.6                              Cotton 0.1     A     45        X            30.3                              Cotton 0.1     A     45             X       29.1                              Cotton 0.01    A     45             X       67.4                              Linen  0.1     A     45   X                 43.2                              Linen  0.1     A     45        X            37.3                              Linen  0.1     A     45             X       37.8                              Wool   0.1     3.5   15             X       22.2                              Wool   0.1     3.5   45   X                 18.6                              Wool   0.1     3.5   45        X            20.0                              Wool   0.1     3.5   45             X       17.8                              Wool   0.1     5.5   45             X       28.0                              Silk   0.1     5.5   15             X       34.9                              Silk   0.1     5.5   45   X                 34.9                              Silk   0.1     5.5   45        X            41.4                              Silk   0.1     5.5   45             X       22.2                              Polyester                                                                            0.1     A     45             X       45.1                              Nylon  0.1     3.5   15             X       41.6                              Nylon  0.1     3.5   45   X                 35.3                              Nylon  0.1     3.5   45        X            35.4                              Nylon  0.1     3.5   45             X       27.8                              Nylon  0.1     5.5   45             X       34.8                              ______________________________________                                         A: pH not adjusted                                                       

Carbon Black Products Example 118

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

4-aminophenyl-2-benzothiazolyl disulfide was prepared according to themethod described in Brzezinska, E.; Temay, Jr., A. L. J. Org. Chem.1994, vol. 59, pp. 8239-8244. 4-aminophenyl-2-benzothiazolyl disulfide(9.79 g) was dissolved in 300 mL of ethanol at 75° C. and added to astirred slurry containing 225 g of carbon black pellets in 1 liter ofethanol and 6.37 g of 70% nitric acid. To the resulting slurry was addeda 10 mL solution of NaNO₂ (2.64 g). Gas was evolved. After stirring for48 hours most of the ethanol had evaporated and the resulting carbonblack product was collected washed with water and dried at 125° C. to aconstant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.77% sulfur, compared to 1.12% for theuntreated black. Therefore, the carbon black product had 0.07 mmol/g ofattached -(4-C₆ H₄)--S--S-(2-C₇ H₅ NS) groups.

Example 119

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

4-aminophenyl-2-benzothiazolyl disulfide (14.1 g) was prepared as inExample 118 and was dissolved in a solution consisting of 10.1 g of 37%HCl, 360 mL of water and 560 mL of acetone. The orange solution was thenadded to a stirred slurry of carbon black pellets in 0.8 liters of waterand 1.2 liters of acetone. A solution of NaNO₂ (3.81 g) in 60 mL ofwater and 90 mL of acetone was added to the slurry in one portion. Gaswas evolved. The slurry was stirred overnight and filtered to collectthe carbon black product. The carbon black product was washed withwater, collected by filtration and dried at 125° C. to a constantweight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.77% sulfur, compared to 1.09% for theuntreated black. Therefore, the carbon black product had 0.07 mmol/g ofattached -(4-C₆ H₄)--S--S--(2-C₇ H₅ NS) groups.

Example 120

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

4-aminophenyl-4'-hydroxyphenyl disulfide was prepared as follows.4-aminophenyl-2-benzothiazolyl disulfide (14.5 g) was dissolved in 325mL of chloroform yielding an orange solution. Over the course of 30minutes a solution of 4-hydroxythiophenol (6.78 g) in 60 mL ofchloroform was added dropwise. After addition was complete, the reactionmixture was stirred overnight The chloroform solution was extracted in aseparatory funnel with a solution of 5.3 g of 37% HCl diluted in 200 mLof water. The aqueous layer was collected, neutralized with 5% NaOH, andextracted with ethyl acetate. The ethyl acetate layer was isolated,dried over MgSO₄ and filtered. Removal of the ethyl acetate gave 10.5 gof 4-aminophenyl-4'-hydroxyphenyl disulfide as a yellow oil.

To a stirred slurry of 4-aminophenyl-4'-hydroxyphenyl disulfide (8.13g), prepared as described above, in 300 mL of water was added a solutionof 6.99 g of 37% HCl in 75 mL of water. The resulting white suspensionwas added to a slurry of 225 g of carbon black pellets in 1.5 liters ofwater and the mixture stirred for 5 minutes. A solution of NaNO₂ (2.64g) in 100 mL of water was added to the slurry. Gas was evolved. Afterstirring the slurry overnight, the carbon black product was isolated byfiltration and washed with water. The carbon black product was thendried at 125° C. to constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.67% sulfur, compared to 1.11% for theuntreated black. Therefore, the carbon black product had 0.09 mmol/g ofattached -(4-C₆ H₄)--S--S--(4-C₆ H₄)-OH groups.

Example 121

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

To a stirred slurry of 237 g of carbon black pellets in 1.4 liters ofwater was added a solution of 4.44 g of 4-aminothiophenol and 7.36 g of37% HCl in 250 mL of water. To the resulting slurry was added a solutionof NaNO₂ (2.78 g) in 75 mL of water. Gas was evolved. The slurry wasstirred for 2.5 hours, filtered, and washed with water. The carbon blackproduct was then dried at 125° C. to constant weight

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.63% sulfur, compared to 1.11% for theuntreated black. Therefore, the carbon black product had 0.15 mmol/g ofattached -(4-C₆ H₄)--SH groups.

Example 122

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

To a stirred slurry of 6-amino-2-mercaptobenzothiazole (6.14 g) in 300mL of water was added 6.99 g of 37% HCl in 75 mL of water. The resultingslurry was cooled to 10° C., and a similarly cooled solution of NaNO₂(2.64 g) in 50 mL of water was added. The resulting orange slurry wasstirred for 30 seconds then added to a stirred slurry of 225 g of carbonblack pellets in 1.4 liters of water and 300 g of ice. Gas was evolved.The slurry was stirred for 2.5 hours and then filtered. The carbon blackproduct was then washed with water and dried at 125° C. to a constantweight

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.98% sulfur, compared to 1.11% for theuntreated black. Therefore, the carbon black product had 0.135 mmol/g ofattached --6-(2--C₇ H₄ NS)--SH groups.

Example 123

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis 2-(4-aminophenyl)ethyl!disulfide was prepared as follows. To arefluxing solution of 4-nitrophenylethylbromide (23 g) in a mixture of280 mL of methanol and 70 mL of water was added a solution of Na₂ S₂O₃.₅ H₂ O (31 g) in 75 mL of water. A further 60 mL of water was thenadded to the reaction mixture. Refluxing conditions were continued for 5hours. The resulting pale yellow solution was allowed to cool to roomtemperature. Methanol was removed from the solution on a rotaryevaporator leaving a white crystalline aqueous slurry. Addition of 300mL of water to the slurry yielded a slightly cloudy solution. To thisaqueous solution of sodium 4-nitrophenylethyl-thiosulfate was added asolution of Na₂ S.9H₂ O (120 g) in 300 mL of water. The reaction mixturerapidly grew cloudy and slightly yellow and, after several minutes ofstirring, a white precipitate formed. This slurry was heated to refluxfor 18 hours then cooled. An orange oil was present which was extractedwith several portions of ethyl acetate. The ethyl acetate extracts werecombined, dried over MgSO₄, and filtered. Removal of the ethyl acetateyielded 12 g of bis 2-(4-aminophenyl)ethyl! disulfide as an orange oil.

To a stirred slurry of bis 2-(4-aminophenyl)ethyl!disulfide (5.02 g),prepared as described above, in 200 mL of water was added a solution of6.67 g of 37% HCl in 100 mL of water. After stirring for 20 minutes anorange solution was obtained and was added to a stirred slurry of carbonblack pellets in 1 liter of water. To the resulting slurry was added asolution of NaNO₂ (2.46 g) in 100 mL of water. Gas was evolved. Afterstirring the slurry overnight, the carbon black product was filtered,washed with water, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.81% sulfur, compared to 1.11% for theuntreated black. Therefore, the carbon black product had 0.11 mmol/g ofattached -(4--C₆ H₄)--CH₂ CH₂ --S--S--CH₂ CH₂ -(4--C₆ H₄)- groups.

Example 124

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis 2-(4-aminophenyl)ethyl!trisulfide was prepared as follows. To aslurry of iron powder (28.4 g) in 300 mL of water at 100° C. in a 500 mLErlenmeyer flask was added 1.42 g of FeSO₄.7H₂ O.4-nitrophenylethylthiosulfate (29 g), prepared according to theprocedure outlined in Example 123, was added to the iron slurry in 1gram portions over the course of 5 minutes while maintaining atemperature of 96°-98° C. During the addition, the flask was manuallyshaken to ensure good mixing. After the addition of4-nitrophenylethylthiosulfate was complete, a further 9.5 g of Fe wasadded and heating continued for 5 minutes. Once the flask had cooled toroom temperature, several drops of conc. NH₄ OH were added to adjust thepH of the reaction mixture from 5 to 9.5. The mixture was then filteredand the iron and iron salts washed with two 50 mL portions of water. Theyellow filtrate was acidified with 37% HCl to a pH of 1. At about a pHof 5, a white precipitate began to form. After cooling the acidifiedfiltrate at 5° C. overnight, the solid was collected by filtration,washed with water then acetone, and air dried. Approximately 14.3 g ofS-(4-aminophenylethyl)thiosulfuric acid was isolated.

To a slurry of 16 g S-(4-aminophenylethyl)thiosulfuric acid in 500 mL ofwater was added solid NaHCO₃ to adjust to pH to 8. As the pH was raisedthe solid dissolved yielding a solution of sodiumS-(4-aminophenylethyl)thiosulfate. To this was added a solution of Na₂S.9H₂ O (12.3 g) in 150 mL of water dropwise over the course of 30minutes with the concomitant formation of a precipitate. After theaddition was complete, the reaction mixture was stirred for 15 minutesand then extracted twice in a separatory funnel with first 200 mL then100 mL of ethyl acetate. The ethyl acetate extracts were combined anddried over MgSO₄. The ethyl acetate was evaporated leaving a yellowsolid. Final isolated yield of bis 2-(4-aminophenyl)ethyl!trisulfide was11.3 g.

To a stirred slurry of bis 2-(4-aminophenyl)ethyl!trisulfide (11.3 g),prepared as described above, in 300 mL of water was added a solution13.7 g of 37% HCl diluted in 100 mL of water. After stirring for 20minutes, an additional 200 mL of water was added and the mixture gentlyheated to 45° C. and stirred for 15 minutes to obtain a solution. Theresulting solution was cooled to room temperature and added to a stirredslurry of carbon black pellets (225 g) in 1.2 liters of water. Next, asolution of NaNO₂ (5.04 g) in 100 mL of water was added to the carbonblack slurry. Gas was evolved. The reaction mixture was stirredovernight and the carbon black product isolated by filtration, washedwith water, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 2.09% sulfur, compared to 1.11% for theuntreated black. Therefore, the carbon black product had 0.07 mmol/g ofattached -(4--C₆ H₄)--2--CH₂ CH₂ --S--S--S--CH₂ CH₂ -(4--C₆ H₄)- groups.

Example 125

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

To a stirred slurry of bis(2-aminophenyl) disulfide in 500 mL of waterwas added a solution of 13.6 g of 37% HCl in 80 mL of water. Theresulting slurry was heated to 65° C. yielding a gold solution with abrown solid. After filtering the hot solution to remove the solid, thesolution was then added with stirring to a room temperature slurry ofcarbon black pellets (225 g) in 1.2 liters of water. A solution of NaNO₂(5.04 g) in 90 mL of water was then added to the carbon black slurryover the course of a minute. Gas was evolved. The mixture was stirredfor 2 hours, filtered and washed with water, and dried at 125° C. to aconstant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.44% sulfur, compared to 1.12% for theuntreated black. Therefore, the carbon black product had 0.05 mmol/g ofattached -(2--C₆ H₄)--S--S-(2--C₆ H₄)- groups.

Example 126

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(3-aminophenyl) disulfide was prepared as follows frombis(3-nitrophenyl) disulfide following a procedure similar to the onedescribed by W. A. Sheppard in Organic Syntheses, Coll. Vol. 5, p. 843.To 13.7 g of solid 3-nitrobenzenesulfonyl chloride was added 46 mL of47% hydriodic acid (HI) yielding a dark brown mixture. The mixture wasrefluxed for 2.5 hours. During the course of the reaction, the iodineby-product sublimed into the water condenser and was removed atappropriate intervals to prevent clogging of the condenser. When thereaction mixture had cooled, NaHSO₃ was added to neutralize theremaining iodine. The resulting slurry was filtered to collect thesolid, and the solid was washed with 200 mL of water. The solid was thenextracted on the filter with 300 mL of acetone yielding an orangesolution. Removal of the acetone gave 8.4 g of bis(3-nitrophenyl)disulfide as a orange solid.

To a stirred slurry bis(3-nitrophenyl) disulfide (8.4 g) in 100 mL ofwater was added a solution of Na₂ S.9H₂ O (20.4 g) in 100 mL of water.The reaction mixture was heated to reflux at which point a dark redsolution was obtained. After refluxing for 18 hours, an additional 5 gof Na₂ S.9H₂ O was added to the reaction mixture and heating continuedfor 2 hours. To the cooled reaction mixture was added 3.5 g of 30% H₂ O₂in a dropwise manner. The white precipitate which formed was extractedtwice with 100 mL of ethyl acetate. The ethyl acetate extracts werecombined and dried over MgSO₄. Removal of the ethyl acetate gave 5.9 gof bis(3-aminophenyl) disulfide.

To a stirred slurry of of bis(3-aminophenyl) disulfide (10.2 g),prepared as described above, in 0.7 liters of water was added a solutionof 18 g of 37% HCl in 50 mL of water. This solution was cooled to 10°C., and a similarly cooled solution of NaNO₂ (6.1 g) in 75 mL of waterthen added. This mixture was then added to a stirred slurry of carbonblack pellets (225 g) in 1.8 liters of water. Gas was evolved Afterstirring for 2 hours, the carbon black product was isolated byfiltration, washed with water and dried at 115° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.71% sulfur, compared to 1.11% for theuntreated black. Therefore, the carbon black product had 0.09 mmol/g ofattached -(3--C₆ H₄)--S--S-(3--C₆ H₄)- groups.

Example 127

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

6-amino-1,2,3-benzothiadiazole was prepared according to the methoddescribed in Ward, E. R; Poesche, W. H.; Higgins, D.; and Heard, D. D.J. Chem. Soc. 1962, pp. 2374-2379. A solution of 3.5 g HCl in 50 mLwater was added to solid 6-amino-1,2,3-benzothiadiazole (2.38 g), andthe resulting solution cooled to 10° C. Next, a cold solution of NaNO₂(1.1 g) in 50 mL was added, and this mixture was then added to a stirredslurry of carbon black pellets (105 g) in 500 mL of water and 100 g ofice. Gas was evolved. After stirring the mixture for 3 hours, the carbonblack product was collected by filtration, washed with water andisopropanol, and air dried to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.50% sulfur, compared to 1.06% for theuntreated black. Therefore, the carbon black product had 0.14 mmol/g ofattached -6-(C₇ H₅ N₂ S) groups.

Example 128

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

N-morpholino-(6-aminobenzothiazole)-2-sulfenamide was prepared asfollows. A solution of NaI₃ was prepared by adding I2 (35.5 g) to anaqueous solution consisting of NaI (47 g) dissolved in 150 mL of water.Next, 6-amino-2-mercaptobenzothiazole (6.5 g) was added to a solutionconsisting of NaOH (2.84 g) in 50 mL of water. After stirring for 15minutes, a red-brown solution was obtained to which morpholine (9.28 g)was added. To this mixture was added the previously prepared NaI₃solution. A brown precipitate formed and the slurry was stirred for 4hours. The solid was isolated by filtration and air dried. The solid wasslurried in 75 mL of ethanol and 3.34 g of morpholine. To this slurrywas added dropwise a solution of 3.24 g of I2 in 60 mL of ethanol overthe course of 20 minutes. After stirring the mixture at room temperatureovernight, the ethanol was removed on a rotary evaporator and theresidue washed with an aqueous solution of NaI to remove unreactediodine. The product was collected by filtration, washed with 250 mL ofwater, and then dried in a vacuum oven at 60° C. for 6 hours. 9.2 g ofN-morpholino-(6-aminobenzothiazole)-2-sulfenamide was isolated in 80%purity.

To a stirred slurry containing carbon black pellets (175 g),N-morpholino-(6-aminobenzothiazole)-2-sulfenamide (7.01 g) and NaNO₂(1.96 g) in 1 liter of water was added a solution consisting of 5.43 gof 37% HCl diluted in 75 mL of water. Gas was evolved. After stirringthe slurry for 48 hours, the carbon black product was filtered, washedwith water, and dried at 100° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.62% sulfur, compared to 1.12% for theuntreated black. Therefore, the carbon black product had 0.08 mmol/g ofattached -6-(2-C₇ H₄ NS)--S--NRR' groups, where RR' is --CH₂ CH₂ OCH₂CH₂ --.

Example 129

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminophenyl) tetrasulfide was prepared as follows. Under anitrogen atmosphere, a solution of 9.74 g of 4-aminothiophenol in 150 mLof anydrous tetrahydrofuran (THF) was prepared. The solution was thencooled in a dry ice/ethanol bath. Butyl lithium was added to the flaskand a thick yellow precipitate formed. Another 125 mL of THF was addedto the flask and the flask warmed in an ice water bath to 5° C. Sulfurmonochloride, S₂ Cl₂, (2.80 mL) was added to the slurry over the courseof 5 seconds resulting in a red solution. After standing overnight at-15° C., the reaction mixture was warmed to room temperature and the THFremoved using a rotary evaporator. The orange oil was redissolved in CH₂C₁₂, filtered through Celite to remove insoluble LiCl and dried overMgSO₄. After filtering the solution to remove the MgSO₄, CH₂ C₁₂ wasremoved yielding 11.4 g of bis(4-aminophenyl) tetrasulfide as an orangeoil.

A solution of 13 g of 37% HCl in 75 mL of water was added to a slurry ofbis(4-aminophenyl) tetrasulfide (10 g), prepared as described above, in200 mL of water, and the resulting mixture was stirred for 15 minutes.The orange-red suspension was cooled to 10° C., and a similarly cooledsolution of NaNO₂ (4.8 g) in 60 mL of water was added over the course of1-2 minutes. The resulting orange-yellow slurry was combined with astirred slurry of carbon black-pellets (213 g) in 1 liter of water and200 g of ice. Gas was evolved. After stirring the mixture overnight, thecarbon black product was isolated by filtration, washed with water, anddried at 120° C. to a constant weight

A sample of the carbon black product which had been extracted with THFovernight and dried contained 2.40% sulfur, compared to 1.23% for theuntreated black. Therefore, the carbon black product had 0.09 mmol/g ofattached -(4-C₆ H₄)--S--S--S--S-(4-C₆ H₄)- groups.

Example 130

This example further illustrates the in situ preparation of a carbonblack product of the present invention A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminophenyl) tetrasulfide was prepared as follows. To a stirredslurry of 4-nitrochlorobenzene (59 g) in 600 mL of water was added asolution consisting of Na₂ S.9H₂ O (240 g) dissolved in 200 mL of water.The resulting mixture was heated to reflux over the course of 45 minutesand continued for 17 hours. At the end of 17 hours a small amount of oilwas present in the flask. After allowing the reaction mixture to cool toroom temperature, the aqueous solution was decanted from the oil andthen filtered. Next, elemental sulfur powder (72 g) was added to theaqueous filtrate and the resulting slurry heated to reflux After 22hours, a large amount of orange oil was present in the reaction. Heatwas removed and the reaction mixture cooled to room temperature. Theorange oil was extracted into 500 mL of ethyl acetate. Once the ethylacetate solution had been filtered and dried over MgSO₄, the ethylacetate was removed to give bis(4-aminophenyl) tetrasulfide as an orangeoil.

Bis(4-aminophenyl) tetrasulfide (10.5 g), prepared as described above,was stirred in 300 mL of water, and to this was added a solution of 13.7g of 37% HCl diluted in 100 mL of water. After stirring 15 minutes, anadditional 200 mL of water was added. Stirring for another 45 minutesyielded a finely divided suspension. The suspension was filtered toremove the solid, and the filtrate was combined with a stirred slurry ofcarbon black pellets (225 g) in 1.2 liters of water. Next, a solution ofNaNO₂ (5.04 g) in 50 mL of water was added to the carbon black slurry.Gas was evolved. After stirring the mixture overnight, the carbon blackproduct was isolated by filtration, washed with water and dried at 120°C. to a constant weight

A sample of the carbon black product which had been extracted with THFovernight and dried contained 2.36% sulfur, compared to 1.09% for theuntreated black. Therefore, the carbon black product had 0.10 mmol/g ofattached -(4-C₆ H₄)--S--S--S--S-(4-C₆ H₄)- groups.

Example 131

A carbon black product having attached -(4-C₆ H₄)--S--S--S--S-(4-C₆ H₄)-groups was prepared by following the method of Example 130 and using asuspension of 7.03 g of 4-aminophenyl tetrasulfide in 200 mL of water, asolution 9.09 g of 37% HCl in 75 mL, a solution of 3.36 g of NaNO₂ in100 mL of water, and a slurry 225 g of the same carbon black pellets in1.2 liters of water.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.63% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.05 mmol/g ofattached -(4-C₆ H₄)--S--S--S--S-(4-C₆ H₄)- groups.

Example 132

A carbon black product having attached -(4-C₆ H₄)--S--S--S--S-(4-C₆ H₄)-groups was prepared by following the method of Example 130 and using asuspension of 5.27 g of 4-aminophenyl tetrasulfide in 200 mL of water, asolution 6.82 g of 37% HCl in 75 mL, a solution of 2.52 g of NaNO₂ in100 mL of water, and a slurry 225 g of the same carbon black pellets in1.2 liters of water.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.54% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.03 mmol/g ofattached -(4-C₆ H₄)--S--S--S--S-(4-C₆ H₄)- groups.

Example 133

A carbon black product having attached -(4-C₆ H₄)--S--S--S--S-(4-C₆ H₄)-groups was prepared by following the method of Example 130 and using asuspension of 3.22 g of 4-aminophenyl tetrasulfide in 200 mL of water, asolution 4.16 g of 37% HCl in 75 mL, a solution of 1.54 g of NaNO₂ in100 mL of water, and a slurry 206 g of the same carbon black pellets in1.2 liters of water.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.26% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.02 mmol/g ofattached -(4-C₆ H₄)--S--S--S--S-(4-C₆ H₄)- groups.

Example 134

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

Liquid 4-aminostyrene (4.02 g) was added to a dilute aqueous acidsolution previously prepared by adding 7.33 g of 37% HCl to 150 mL ofwater. After stirring the mixture for 5 minutes, a yellow solution wasobtained and added to stirred slurry of carbon black pellets (225 g) in1.2 liters of water. Addition of a solution of NaNO₂ (2.94 g) dissolvedin 50 mL of water resulted in the formation of gas. After stirring themixture for 3 hours, the carbon black product was isolated byfiltration, washed with water, and dried at 125° C. to a constantweight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 0.46% hydrogen, compared to 0.37% for theuntreated black. Therefore, the carbon black product had 0.06 mmol/g ofattached -(4-C₆ H₄)--CH═CH₂ groups.

Example 135

This example further illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

S-(4-aminophenyl)thiosulfuric acid (6.60 g) was prepared by the methoddescribed in Tanaka et al, Chem: Pharm. Bull. 1974, vol. 22, p. 2725,and was dissolved in 600 mL of water containing 3.50 g of 37% HCl. Thissolution was added to a stirred slurry of carbon black pellets (215 g)in 1.2 liters of water. Next, an aqueous solution of NaNO₂ (2.52 g) in30 mL of water was added to the slurry. Gas was evolved. After stirringthe mixture for 2 hours then standing overnight, the carbon blackproduct was isolated by filtration, washed with water, and dried at 125°C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.58% sulfur, compared to 1.23% for theuntreated black. Therefore, the carbon black product had 0.05 mmol/g ofattached -(4-C₆ H₄)--S--SO₃ H groups.

Example 136

This example futher illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis 4-(4'-aminobenzenesulfonamido)phenyl! disulfide was prepared asfollows. To N-acetylsulfanilyl chloride (20.0 g) stirring in acetone(500 mL) at room temperature was added 4-aminophenyl disulfide (10.12 g)followed by pyridine (7.09 g). The cloudy yellow-orange reaction mixturewas allowed to stir for 20 hours, during which time a clear, goldenyellow solution formed. 7.5 mL of 37% HCl was added to 45 mL of water,and this acid solution was added to the reaction mixture. The acetonewas removed, and the remaining mixture was diluted with 100 mL of waterand extracted with ethyl acetate (2×200 mL). The combined ethyl acetateextracts were washed with water (5×100 mL), washed with a saturatedbrine solution (1×100 mL), dried over Na₂ SO₄, and filtered. Removal ofthe ethyl acetate yielded 29.37 g of crude product as a tan foam. Thismaterial was added to a flask containing THF (150 mL), and 2N HCl (150mL) was added. The resulting slurry was heated to reflux. After 24 hoursat reflux, 48 mL of 2N HCl were added, and the reaction was continued atreflux for 22 hours. The clear orange solution was allowed to cool toroom temperature and carefully made basic with solid NaHCO₃, and theresulting mixture extracted with ethyl acetate (3×200 mL). The combinedethyl acetate extracts were washed with water (4×200 mL) until neutral,dried over Na₂ SO₄, and filtered. Removal of the ethyl acetate yielded20.2 g of the desired product as a yellow solid.

Bis 4-(4'-aminobenzenesulfonamido)phenyl!disulfide (18.83 g), preparedas described above, was dissolved in a mixture of 500 mL of water, 632.4g of acetone, and 13.65 g of 37% HCl. This yellow solution was cooled inan ice water bath, and NaNO₂ (13.65 g) was added, yielding a deep redsolution containing an orange precipitate. This mixture was added in oneportion to a rapidly stirring slurry of carbon black pellets (225 g) in1/1 acetone/water (1.5 liters total). Gas was evolved. The slurry wasstirred overnight and filtered to collect the carbon black product. Thecarbon black product was washed with water, collected by filtration, anddried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with TBFovernight and dried contained 2.21% sulfur, compared to 1.14% for theuntreated black. Therefore, the carbon black product had 0.084 mmol/g ofattached -(4-C₆ H₄)--SO₂ NH-(4-C₆ H₄)--S--S-(4-C₆ H₄)--NHSO₂ -(4-C₆ H₄)-groups.

Example 137

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

p-Phenylenediamine (4.87 g) was dissolved in 250 mL of water containing9.11 g of 37% HCl. This was cooled in an ice bath, and a solution of3.36 g NaNO₂ dissolved in 125 mL of water was added. The resultingblue-green solution was added in one portion to a rapidly stirringslurry of carbon black pellets (225 g) in 2 liters of water containing280 g of ice. The slurry was stirred overnight and filtered to collectthe carbon black product. This product was washed with water, collectedby filtration, and dried at 125° C. to a constant weight.

Example 138

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

p-Phenylenediamine (2.43 g) was dissolved in 250 mL of water containing9.11 g of 37% HCl. This was cooled in an ice bath, and a solution of3.36 g NaNO₂ dissolved in 125 mL of water was added. This blue-greensolution was added in one portion to a rapidly stirring slurry of carbonblack pellets (225 g) in 2 liters of water containing 280 g of ice. Theslurry was stirred overnight and filtered to collect the carbon blackproduct. This product was washed with water, collected by filtration,and dried at 125° C. to a constant weight.

Example 139

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

2,2'-bis(6-aminobenzothiazolyl) disulfide was prepared as follows.6-Amino-2-mercaptobenzothiazole (15.0 g) was added to 500 mL of water.To this slurry was added a solution of NaOH (3.3 g) dissolved in 1 literof water, and the mixture stirred for 1 hour at room temperature untilmost of the thiol was dissolved. A solution containing NaI (24.73 g) and12 (10.47 g) in 750 mL of water was added to the thiolate solutiongradually over 1.5 hours with vigorous stirring. During the addition, athick slurry containing a yellowish solid formed. After the addition andcontinued stirring for an additional 45 minutes, the solid was isolatedby filtration.

2,2'-bis(6-aminobenzothiazolyl)-disulfide (12.23 g), prepared asdescribed above, was added to 600 mL of water containing 13.66 g of 37%HCl. This yellow slurry was cooled in an ice bath, and a solution of5.04 g NaNO₂ dissolved in 50 mL of water was added. The resulting darkbrown mixture was added in one portion to a rapidly stirring slurry ofcarbon black pellets (225 g) in 2 liters of water containing 280 g ofice. The slurry was stirred overnight and filtered to collect the carbonblack product The product was washed with water and isopropanol,collected by filtration, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.69% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.054 mmol/g ofattached -6-(2-C₇ H₄ NS)--S--S-2-(6-C₇ H₄ NS)- groups.

Example 140

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

4-arninophenyl-4-aminobenzyl sulfide was prepared as follows. A solutionof NaOH (7.1 g) in water (200 mL) was added to a mixture of4-arninothiophenol (19.8 g) in 190 mL of water. The mixture was stirreduntil most of the thiophenol was dissolved. To this mixture was added4-nitrobenzyl chloride (25.8 g) in portions with good stirring. Theresulting yellow solution was then stirred at reflux for 1.5 hours,during which time a thick red oil separated. At the end of the reaction,the mixture was allowed to cool to room temperature, and the red oilseparated as a waxy solid. The solid was extracted with ethyl acetate(400 mL followed by 100 mL), and the combined ethyl acetate extractswere dried over Na₂ SO₄ and filtered. Removal of the ethyl acetateyielded 38.65 g of 4-aminophenyl4-nitrobenzyl sulfide.

All of the above product was dissolved in a mixture of ethanol (235 mL)and water (780 mL). To this solution was added 37% HCl (27.83 g) andiron powder (49.78 g), and the slurry stirred at reflux for 3 hours.After cooling to room temperature, 200 mL of water were added, and themixture was extracted with ethyl acetate (600 mL followed by 200 mL).The combined ethyl acetate extracts were dried over Na₂ SO₄ andfiltered. Removal of the ethyl acetate yielded 31.53 g of the desiredproduct.

4-aminophenyl-4-arninobenzyl sulfide (7.77 g), prepared as describedabove, was added to 250 mL of water containing 13.7 g of 37% HCl. Theresulting solution was cooled in an ice bath and a solution of 5.04 gNaNO₂ dissolved in 125 mL of water added. The resulting mixture wasadded in one portion to a rapidly stirring slurry of carbon blackpellets (225 g) in 2 liters of water containing 280 g of ice. The slurrywas stirred overnight and filtered to collect the carbon black product.This product was collected by filtration, washed with water then withethanol, collected by filtration, and dried at 125° C. to a constantweight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.38% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.12 mmol/g ofattached -(4-C₆ H₄)--S--CH₂ -(4-C₆ H₄)- groups.

Example 141

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminophenyl)thiosulfonate was prepared following a modifiedprocedure to the one described in Leitch, L.; Baker, B.; Brickman, L.Can. J. Res. Sect. B 1945, 23, 139. To a well-stirred mixture ofthiourea (11.4 g) in acetone (175 mL) was added pyridine (16.85 mL)followed by N-acetylsulfanilyl chloride (35.05 g). A yellow colordeveloped. This mixture was heated to reflux and stirred under theseconditions for 80 minutes. The reaction was then allowed to cool to roomtemperature, and a fluffy solid precipitated. After removing theacetone, 500 mL of hot water were added. A pale yellow precipitateformed, which was isolated by filtration, yielding 22.7 g ofbis(4-acetamidophenyl)thiosulfonate.

The desired final product was obtained following a modification to theprocedure described in Bere, C.; Smiles, S. J. Chem. Soc. 1924, 2359.All of the bis-(4-acetamidophenyl)thiosulfanate prepared above (22.7 g)was dissolved in 250 mL of THF, and 250 mL of 2N HCl was added. Themixture was heated to reflux and stirred for 5 hours. After allowing thereaction to cool to room temperature, most of the THF was removed andsolid NaHCO₃ added carefully until no futher gas evolution was seen. Anorange precipitate formed, which was isolated by filtration, yieldingthe desired bis(4-aminophenyl)thiosulfonate (10.3 g).

Bis(aminophenyl)thiosulfonate (9.46 g), prepared as described above, wasadded to 250 mL of water containing 13.65 g of 37% HCl, and the cloudyyellow mixture cooled in an ice bath. To this was added a solution of5.04 g NaNO₂ dissolved in 125 mL of water. A yellow colloidal suspensionformed. The resulting mixture was added in one portion to a rapidlystirring slurry of carbon black pellets (225 g) in 2 liters of watercontaining 280 g of ice. The slurry was stirred overnight and filteredto collect the carbon black product. The product was washed with waterand collected by filtration. This was then washed with ethanol,collected by filtration, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.85% sulfur, compared to 1.30% for theuntreated black. Therefore, the carbon black product had 0.086 mmol/g ofattached -(4-C₆ H₄)--SO₂ --S-(4-C₆ H₄)- groups.

Example 142

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminobenzyl) sulfide was prepared as follows. A solution of4-nitrobenzyl chloride (55.0 g) in 500 mL of THF was added slowly, withgood stirring, to a solution of Na₂ S.₉ H₂ O (43.2 g) in 1 liter ofwater. The mixture was stirred at room temperature for 18 hours. Removalof the THF and filtration yielded 46.8 g of bis(4-nitrobenzyl) sulfide.

All of this material was dissolved in 530 mL of ethanol. Water (1.1liters) was added followed by 530 mL of 2N HCl and 69.1 g of ironpowder. While stirring vigorously, the mixture was heated at reflux for3 hours. After cooling to room temperature, 800 mL of water were added,and the reaction mixture was extracted with 1900 mL of ethyl acetate inseveral portions. The combined ethyl acetate extracts were dried overNa₂ SO₄, and filtered. Removal of the ethyl acetate yielded 28.9 g ofthe desired bis(4-aminobenzyl) sulfide.

Bis(4-aminobenzyl) sulfide (12.8 g), prepared as described above, wasadded to 700 mL of water containing 21.3 g of 37% HCl. The resultingsolution was stirred for 2 hours and then cooled in an ice bath. Asolution of 7.84 g NaNO₂ dissolved in 75 mL of water was added. Theresulting brown colloidal suspension was added in one portion to arapidly stirring slurry of carbon black pellets (350 g) in 2.5 liters ofwater containing 280 g of ice. The slurry was stirred overnight and thenfiltered to collect the carbon black product. This product was washedwith ethanol then with water, collected by filtration, and dried at 125°C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.34% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.11 mmol/g ofattached -(4-C₆ H₄)--CH₂ --S--CH₂ -(4-C₆ H₄)- groups.

Example 143

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminobenzyl) sulfide (10.99 g), prepared as described for Example142 ove, was added to 700 mL of water containing 18.2 g of 37% HCl.After stirring for 2 hours, the solution was cooled in an ice bath. Asolution of 6.72 g NaNO₂ dissolved in 75 mL of water was added. Theresulting brown colloidal suspension was added in one portion to arapidly stirring slurry of carbon black pellets (225 g) in 2 liters ofwater containing 280 g of ice. The slurry was stirred overnight andfiltered to collect the carbon black product. This product was washedwith ethanol then with water, collected by filtration, and dried at 125°C. to a constant weight

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.40% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.125 mmol/g ofattached -(4-C₆ H₄)--CH₂ --S--CH₂ -(4-C₆ H₄)- groups.

Example 144

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(3-aminobenzyl) sulfide was prepared as follows. A solution of3-nitrobenzyl chloride (55.0 g) in 500 mL of THF was added to a solutionof Na₂ S.9H₂ O (43.2 g) in 1 liter of water slowly with good stirring.This mixture was stirred at room temperature for 18 hours. Removal ofthe THF and filtration yielded 45.8 g of bis(3-nitrobenyl) sulfide.

All of this material was dissolved in 530 mL of ethanol. 1.1 liters ofwater was added followed by 140 mL of 2N HCl and 67.64 g of iron powder.While stirring vigorously, the mixture was heated to reflux for 4.5hours. More iron powder (15.0 g) was added, and the reaction wascontinued at reflux for an additional 1 hour. After cooling to roomtemperature, the reaction mixture was extracted several times with ethylacetate. The combined ethyl acetate extracts were dried over Na₂ SO₄,and filtered. Removal of the ethyl acetate yielded 33.1 g of the desiredbis(3-aminobenzyl) sulfide.

Bis(3-aminobenzyl) sulfide (10.99 g), prepared as described above, wasadded to 400 mL of water containing 18.2 g of 37% HCl. After stirringfor 2 hours, the solution was cooled in an ice bath. A solution of 6.72g NaNO₂ dissolved in 75 mL of water was added. The resulting browncolloidal suspension was added in one portion to a rapidly stirringslurry of carbon black pellets (225 g) in 2 liters of water containing280 g of ice. The slurry was stirred overnight and filtered to collectthe carbon black product. The product was washed with ethanol then withwater, collected by filtration, and dried at 125° C. to a constantweight

A sample of the carbon black product which had been extracted with THFovernight and dired contained 1.50% sulfur, compared to 1.21% for theuntreated black. Therefore, the carbon black product had 0.09 mmol/g ofattached -(3-C₆ H₄)--CH₂ --S--CH₂ -(3-C₆ H₄)- groups.

Example 145

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine nurnberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(3-aminobenzyl) sulfide (16.48 g), prepared as described for Example144 above, was added to 500 mL of water containing 27.32 g of 37% HCl.After stirring for 2 hours, the solution was cooled in an ice bath. Asolution of 10.1 g NaNO₂ dissolved in 75 mL of water was added. Theresulting brown colloidal suspension was added in one portion to arapidly stirring slurry of carbon black pellets (450 g) in 3 liters ofwater containing 300 g of ice. The slurry was stirred overnight andfiltered to collect the carbon black product. This product was washedwith ethanol then with water, collected by filtration, and dried at 125°C. to a constant weight

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.30% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.094 mmol/g ofattached -(3-C₆ H₄)--CH₂ --S--CH₂ -(3-C₆ H₄)- groups.

Example 146

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-arninobenzyl) disulfide was prepared as follows. A mixture of4-nitrobenzyl chloride (40.0 g) in 933 mL of methanol and 233 mL orwater was heated until a solution formed. To this was added slowly, withgood stirring, a solution of Na₂ S₂ O₃.5H₂ O (72.34 g) in 233 mL ofwater. This mixture was then stirred at reflux for 4 hours. Aftercooling to room temperature, most of the methanol was removed, and tothe aqueous solution (approximately 300 mL) was added a solution of Na₂CO₃ in 600 mL of water. This was stirred at room temperature for 18hours, during which time a cream colored opaque mixture formed. Theprecipitate was isolated by filtration and washed with water yielding37.1 g of bis(4-nitrobenzyl) disulfide.

Bis(4-nitrobenzyl) disulfide (10.0 g) was dissolved in 1.5 liters ofethanol (heating to approximately 73° C. followed by filtration wasneeded in order to obtain a clear solution). To this heated solution wasadded 0.5 liters of water, 30 mL of 2N HCl, and 16.4 g of iron powder.The temperature was then allowed to drop to approximately 45° C., andthe reaction was continued at this temperature for 8 hours. The reactionmixture was then heated to reflux and allowed to continue for 3.5 hours.After cooling to room temperature, the mixture was then extractedseveral times with ethyl acetate. The combined ethyl acetate extractswere dried over Na₂ SO₄, and filtered. Removal of the ethyl acetateyielded 4.69 g of the desired bis(4-aminobenzyl) disulfide.

Bis(4-aminobenyl) disulfide (9.32 g), prepared as described above, wasadded to 250 mL of water containing 13.66 g of 37% HCl. After stirringfor 2 hours, the solution was cooled in an ice bath. A solution of 5.04g NaNO₂ dissolved in 125 mL of water was added. This mixture was addedin one portion to a rapidly stirring slurry of carbon black pellets (225g) in 2 liters of water containing 280 g of ice. The slurry was stirredovernight and filtered to collect the carbon black product. The productwas washed with ethanol then with water, collected by filtration, anddried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.55% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.086 mmol/g ofattached -(4-C₆ H₄)--CH₂ --S--S--CH₂ -(4-C₆ H₄)- groups.

Example 147

This example further illustrates the preparation of a carbon blackproduct of the present nvention. A carbon black with an iodine number of120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(3-aminobenzyl) disulfide was prepared as follows. A solution of Na₂S₂ O₃.5H₂ O (72.34 g) in 233 mL of water was added slowly, with goodstirring, to a solution of 3-nitrobenzyl chloride (40.0 g) in 933 mL ofmethanol and 233 mL of water. The resulting mixture was then stirred atreflux for 4 hours. After cooling to room temperature, most of themethanol was removed, and the aqueous layer was extracted with ethylacetate. Removal of the water from the aqueous layer yielded 69.04 g ofthe sodium salt of 3-nitrobenyl thiosulfate.

A solution of Na₂ CO₃ (124.83 g) in 1 liter of water was gradually addedto a solution of the sodium salt of 3-nitrobenzyl thiosulfate (39.21 g)in 800 mL of water with good stirring. After stirring at roomtemperature for 18 hours, a cream colored opaque mixture formed. Theprecipitate was isolated by filtration and washed with water yielding16.8 g of bis(3-nitrobenzyl) disulfide.

Bis(3-nitrobenzyl) disulfide (7.5 g) was dissolved in 1.5 liters ofethanol (this was heated and then filtered while warm in order to obtaina clear solution). To this heated solution was added 750 mL of water,22.5 mL of 2N HCl, and 12.3 g of iron powder. The reaction was thenfurther heated to just below the reflux temperature, and heating wascontinued for 5 hours. After cooling to room temperature, 400 mL ofwater was added, and the mixture was then extracted several times withethyl acetate. The combined ethyl acetate extracts were dried over Na₂SO₄, and filtered. Removal of the ethyl acetate yielded 5.15 g of thedesired bis(3-aminobenzyl) disulfide.

Bis(3-arninobenzyl) disulfide (9.99 g), prepared as described above, wasadded to 250 mL of water containing 14.6 g of 37% HCl. After stirringfor 2 hours, the solution was cooled in an ice bath. A solution of 5.4 gNaNO₂ dissolved in 125 mL of water was added. This mixture was added inone portion to a rapidly stirring slurry of carbon black pellets (241 g)in 2 liters of water containing 280 g of ice. The slurry was stirredovernight and filtered to collect the carbon black product. This productwashed with ethanol then with water, collected by filtration, and driedat 125° C. to a constant weight.

A sample of the carbon black product which had been extracted withovernight and dried contained 1.62% sulfur, compared to 1.00% for theuntreated black. Therefore, the carbon black product had 0.097 mmol/g ofattached -(3-C₆ H₄)--CH₂ --S--S--CH₂ -(3-C₆ H₄)- groups.

Example 148

This example further illustrates the in situ method of preparation of acarbon black product of the present invention. A carbon black with aniodine number of 120 mg/g and a DBPA of 125 mL/100 g was used.

N-morpholino-(4-aminophenyl)sulfenamide was prepared as follows. Asolution of I2 (14.2 g) in ethanol (300 mL) was added to a well-stirredsolution containing 4-diaminophenyl disulfide (13.9 g) and morpholine(24.4 g) in ethanol (300 mL). The reaction mixture was stirred at roomtemperature for 3 hours. Removal of the ethanol gave a thick, nearlyblack oil. It was redissolved in 750 mL of ethyl acetate and washedseveral times with water. The ethyl acetate layer was dried over Na₂SO₄, and filtered. Removal of the ethyl acetate yielded 19.6 g of thedesired N-morpholino-(4-aminophenyl)sulfenamide.

N-morpholno-(4-aminophenyl)sulfenamide (9.46 g), prepared as describedabove, was added to a well-stirred mixture of carbon black (225 g), ice(280 g), and water (2 liters). To this was added a solution of 3.36 gNaNO₂ dissolved in 75 mL of water followed by addition of a solution of37% HCl (4.66 g) in 75 mL of water. The slurry was stirred for 5 hours,filtered to collect the carbon black product, and dried at 125° C. to aconstant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.26% sulfur, compared to 1.21% for theuntreated black. Therefore, the carbon black product had 0.02 mmol/g ofattached -(4-C₆ H₄)--S--NRR' groups where RR' is --CH₂ CH₂ OCH₂ CH₂ --.

Example 149

This example further illustrates the in situ method of preparation of acarbon black product of the present invention. A carbon black with aniodine number of 120 mg/g and a DBPA of 125 mL/100 g was used.

N-morpholino-(4-aminophenyl)sulfenamide (9.46 g), prepared as describedfor Example 148 above, was added to a well-stirred mixture of carbonblack (225 g), ice (280 g), and water (2 liters). To this was added asolution of 3.36 g NaNO₂ dissolved in 75 mL of water followed byaddition of a solution of 37% HCl (9.32 g) in 75 mL of water. The slurrywas stirred for 5 hours, filtered to collect the carbon black product,and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.34% sulfur, compared to 1.21% for theuntreated black. Therefore, the carbon black product had 0.04 mmol/g ofattached -(4-C₆ H₄)--S--NRR' groups where RR' is --CH₂ CH₂ OCH₂ CH₂ --.

Example 150

This example further illustrates the method of preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis 2-(4-aminobenzenesulfonamido)ethyl! disulfide was prepared asfollows. To a well-stirred mixture of N-acetylsulfanilyl chloride (1.26g) in 50 mL of CH₂ C₁₂ in an ice bath was added triethylamine (559 mg)followed by cystamine (2,2'-diaminoethyl disulfide, 400 mg). The icebath was removed, and the reaction was stirred for 18 hours at roomtemperature. Removal of the CH₂ C₁₂ gave a brownish-yellow solid, whichwas stirred vigorously in 50 mL of water for 3 hours and filtered togive 1.24 g of bis 2-(4-acetamidobenzenesulfonamido)ethyl! disulfide.

A sample of bis 2-(4-acetamidobenzenesulfonamido)ethyl! disulfide (1.00g) was heated to reflux in a mixture of 40 mL of ethanol and 40 mL of 2NHCl, and stirred at this temperature for 3 hours. After cooling to roomtemperature, 200 mL of water were added and the mixture made basic bycarefully adding solid NaHCO₃. A white precipitate formed which wasisolated by extraction of the basic aqueous layer with ethyl acetate(2×150 mL). The combined ethyl acetate extracts were dried over Na₂ SO₄and filtered. Removal of the ethyl acetate yielded 735 mg of the desiredbis 2-(4-aminobenzenesulfonamido)ethyl! disulfide.

Bis 2-(4-aminobenzenesulfonamido)ethyl! disulfide (15.6 g), prepared asdescribed above, was added to 275 mL of water containing 13.6 g of 37%HCl and the mixture cooled in an ice bath. Next, a solution of 5.04 gNaNO₂ dissolved in 60 mL of water was added to the mixture. Theresulting yellow slurry was added in one portion to a rapidly stirringslurry of carbon black pellets (225 g) in 1.2 liters of water. Theslurry was stirred overnight and filtered to collect the carbon blackproduct. This product was washed with water, collected by filtration,and dried at 100° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 2.06% sulfur, compared to 1.21% for theuntreated black. Therefore, the carbon black product had 0.07 mmol/g ofattached -(4-C₆ H₄)--SO₂ NH--CH₂ CH₂ --S--S--CH₂ CH₂ --NHSO₂ -(4-C₆ H₄)-groups.

Example 151

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

2-(4-aminophenyl)-1,3-dithiane was prepared following a modification tothe procedure described in Truce, W.; Roberts, F. J. Org. Chem. 1963,28, 961. To a well-stirred mixture of 4-acetamidobenzaldehyde (12.7 g)in 200 mL of acetic acid was added MgCl₂ (5.57 g) followed by1,3-propane dithiol (8.44 g). The reaction mixture turned white uponaddition of the dithiol. This mixture was stirred at room temperaturefor 2 hours. The white precipitate was isolated by filtration, washedseveral times with water, and dried to give 12.5 g of2-(4-acetamidophenyl)-1,3-dithiane.

All 12.5 g of 2-(4-acetamidophenyl)-1,3-dithiane was dissolved in 150 mLof ethanol. A total of 150 mL of 2N HCl was added, and the reactionmixture was heated to reflux. After reacting at this temperature for 6hours, the clear yellow solution was allowed to cool to room temperatureand then made basic with a dilute NaOH solution. The resulting lightyellow precipitate was isolated by filtration, washed with water untilneutral, and dried to yield 14.8 g of the desired2-(4-aminophenyl)-1,3-dithiane.

2-(4-aminophenyl)-1,3-dithiane (7.13 g), prepared as described above,was added to 250 mL of water containing 6.83 g of 37% HCl and was cooledin an ice bath. A solution of 2.52 g NANO₂ dissolved in 125 mL of waterwas added. This mixture was added in one portion to a rapidly stirringslurry of carbon black pellets (225 g) in 2 liters of water containing200 g of ice. The slurry was stirred for 4.5 hours and filtered tocollect the carbon black product. This product was washed with water,collected by filtration, and dried at 25° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.65% sulfur, compared to 1.21% for theuntreated black. Therefore, the carbon black product had 0.07 mmol/g ofattached -(4-C₆ H₄)-2-(1,3-dithiane) groups.

Example 152

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

2-(4-aminophenyl)-1,3-dithiane (4.75 g), prepared as described inExample 151 above, was added to 250 mL of water containing 4.55 g of 37%HCl. Next, the mixture was cooled in an ice bath and a solution of 1.68g NaNO₂ dissolved in 125 mL of water was added. The resulting mixturewas added in one portion to a rapidly stirring slurry of carbon blackpellets (112.5 g) in 2 liters of water containing 100 g of ice. Theslurry was stirred for 4.5 hours and filtered to collect the carbonblack product. This product was washed with water, collected byfiltration, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.47% sulfur, compared to 1.21% for theuntreated black. Therefore, the carbon black product had 0.04 mmol/g ofattached -(4-C₆ H₄)-2-(1,3-dithiane) groups.

Example 153

This example futher illustrates the in situ preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

N,N'-bis-(4-arninophenyl)-piperazinosulfenamide was prepared as follows.A solution of I2 (21.6 g) in 800 mL of ethanol was added to awell-stirred solution of 4,4-diaminophenyldisulfide (21.3 g) andpiperazine (36.7 g) in 1 liter of ethanol at room temperature. The darkcolored reaction mixture was stirred at this temperature for 16 hoursand then filtered. The cream colored precipitate was washed with waterand filtered to yield 25.1 g of the desiredN,N'-bis-(4-aminophenyl)-piperazinosulfenamide.

N,N'-bis-(4-aminophenyl)-piperazinosulfenamide (11.2 g), prepared asdescribed above, was added to a well-stirred mixture of carbon black(225 g), ice (280 g), and water (2 liters). To this was added a solutionof 5.04 g NaNO₂ dissolved in 75 mL of water followed by a solution of37% HCl (13.65 g) in 75 mL of water. The slurry was stirred overnightand filtered to collect the carbon black product. The product was washedwith water, filtered, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.91% sulfur, compared to 1.21% for theuntreated black. Therefore, the carbon black product had 0.11 mmol/g ofattached -(4-C₆ H₄)--S-(1,4-C₄ H₈ N₂)--S-(4-C₆ H₄)- groups.

Example 154

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminophenyl) disulfide (4.19 g) was dissolved in 230 mL of watercontaining 7.32 g of 37% HCl. The solution was then cooled in an icebath and a solution of 2.64 g NaNO₂ dissolved in 40 mL of water added.This mixture was added in one portion to a rapidly stirring slurry ofcarbon black pellets (225 g) in 1200 mL of water containing a smallamount of ice. The slurry was stirred for 2 hours and filtered tocollect the carbon black product. This product was washed with ethanol,then with water, collected by filtration, and dried at 125° C. to aconstant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.55% sulfur, compared to 1.10% for theuntreated black. Therefore, the carbon black product had 0.07 mmol/g ofattached -(4-C₆ H₄)--S--S-(4-C₆ H₄)- groups.

Example 155

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminophenyl) disulfide (8.55 g) was dissolved in 180 mL of watercontaining 14.65 g of 37% HCl. The solution was then cooled in an icebath and 50 mL of ethanol was added followed by addition of a solutionof 5.28 g NaNO2 dissolved in 35 mL of water. This mixture was added inseveral portions to a rapidly stirring slurry of carbon black pellets(225 g) in 1200 mL of water containing a small amount of ice. The slurrywas stirred for 2 hours and filtered to collect the carbon blackproduct. This product was washed with ethanol, then with water,collected by filtration, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 1.82% sulfur, compared to 1.10% for theuntreated black. Therefore, the carbon black product had 0.11 mmol/g ofattached -(4-C₆ H₄)--S--S-(4-C₆ H₄)- groups.

Example 156

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminophenyl) disulfide (11.18 g) was dissolved in 560 mL of watercontaining 19.53 g of 37% HCl. The solution was cooled in an ice bathand a solution of 7.04 g NaNO2 dissolved in 60 mL of water added. Anadditional 150 mL of water was added, and the mixture added in oneportion to a rapidly stirring slurry of carbon black pellets (225 g) in1200 mL of water containing a small amount of ice. The slurry wasstirred for 2 hours and filtered to collect the carbon black product.This product was washed with ethanol, then with water, collected byfiltration, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 2.26% sulfur, compared to 1.10% for theuntreated black. Therefore, the carbon black product had 0.18 mmol/g ofattached -(4-C₆ H₄)--S--S-(4-C₆ H₄)- groups.

Example 157

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminophenyl) disulfide (13.97 g) was dissolved in 560 mL of watercontaining 24.4 g of 37% HCl. The solution was cooled in an ice bath anda solution of 8.80 g NaNO2 dissolved in 60 mL of water added. Anadditional 150 mL of water was added and the resulting mixture added inone portion to a rapidly stirring slurry of carbon black pellets (225 g)in 1200 mL of water containing a small amount of ice. The slurry wasstirred for 3.5 hours and filtered to collect the carbon black product.This product was washed with ethanol, then with water, collected byfiltration, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 2.50% sulfur, compared to 1.10% for theuntreated black. Therefore, the carbon black product had 0.22 mmol/g ofattached -(4-C₆ H₄)--S--S-(4-C₆ H₄)- groups.

Example 158

This example further illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 mL/100 g was used.

Bis(4-aminophenyl) disulfide (17.1 g) was dissolved in 175 mL of watercontaining 29.30 g of 37% HCl. The resulting solution was cooled in anice bath and a solution of 10.6 g NaNO2 dissolved in 60 mL of wateradded. 100 mL of ethanol was added, and this mixture was added in oneportion to a rapidly stirring slurry of carbon black pellets (225 g) in1200 mL of water containing a small amount of ice. The slurry wasstirred for 2 hours and filtered to collect the carbon black product.This product was washed with ethanol, then with water, collected byfiltration, and dried at 125° C. to a constant weight.

A sample of the carbon black product which had been extracted with THFovernight and dried contained 2.55% sulfur, compared to 1.10% for theuntreated black. Therefore, the carbon black product had 0.23 mmol/g ofattached -(4-C₆ H₄)--S--S-(4-C₆ H₄)- groups.

Example 159--Comparative Carbon Black Products

In this comparative example, the carbon black used in Example 118-158was washed with water, ethanol and water and subsequently dried to givethe comparative carbon black product.

Example 160--Comparative Carbon Black Products

In this comparative example, the carbon black used in Examples 118-158was used without modification and serves as the comparative carbon blackproduct.

Use of carbon black products in rubber formulations

The carbon black products described in Examples 118-158 can be used in avariety of elastomers. The elastomers include, but are not limited to,the following types: solution SBR, functionalized (tin coupled and/orchemically modified and/or other functional-ization) solution SBR,natural rubber, emulsion SBR, polybutadiene, and terpolymers. Theseelastomers may appear in rubber formulations alone or as blends.

NS 116 and NS 114 are chemically modified tin coupled solution SBRsavailable from Nippon Zeon, Japan. Duradene 715 is a solution SBR.Duradene is a registered trademark for SBR products available fromFirestone, Akron Ohio. S 1216 is a solution SBR available from GoodyearTire and Rubber Co., Akron Ohio. SBR-1500 is an emulsion SBR availablefrom Copolymer Rubber and Chemical Corp., Baton Rouge, La. SL-574 is atin coupled solution SBR available from Japan Synthetic Rubber Co.(JSR), Japan. RCTOS86 and T0587 are chemically modified solution SBRsalso available from JSR. Flexzone is a registered trademark forantidegradent products available from Uniroyal Chemical, Naugatuck,Conn. CBS is N-cyclohexylbenzothiazylsulfenamide, MBT is2-mercaptobenzothiazole and DTDM is N,N'-dithiodimorpholine.

Examples 161-166

These examples illustrate the use of the carbon black products ofExamples 118, 121, 122 and the comparative Example 160 in two differentrubber formulations. The polymer was milled in a Brabender mixer for 1minute at 100° C. The carbon black product or comparative carbon blackwas added and mixed for 3 additional minutes or until a temperature of160° C. was reached. The mixture was then dumped and passed through anopen mill 3 times. After allowing the compound to stand at roomtemperature for 2 hours, it was transferred back into the Brabender andmixed for 1 minute at 100° C. After 1 minute, ZnO and stearic acid wereadded and mixed for 2 minutes and then Flexzone 7P antidegradent wasadded and mixed for an additional minute or until a temperature of 160°C. was reached. The sample was then dumped, passed through an open mill3 times and allowed to stand at room temperature for 2 hours. The samplewas placed back into the Brabender and mixed for 1 minute at 100° C. Thecuratives were then added and mixed for 1 minute and the sample thendumped and passed through an open mill 3 times. The formulations usedwere selected from Table I.

The data in Table II show that carbon black products of the presentinvention are useful in rubber formulations. In the case where a blendof NS-116 and NS-114 was used, significant increases in 100% modulus,bound rubber, tensile strength, hardness and abrasion resistance can beobtained, as can significant decreases in Tan δ. In Duradene 715, highermodulus, hardness, and bound rubber are obtained, while tensilestrength, elongation at break and 70° C. Tan δ are reduced. Themagnitude of the effect depends on the specific groups attached to thecarbon black product.

Examples 167-180

These examples illustrate the use of the carbon black products ofExamples 121-124 and the comparative Example 160 in several differentrubber formulations. With the exception of those formulations containingDTDM, rubber compounds were prepared by the method described forExamples 161-166 using formulations selected from Table I. A slightchange in the mixing procedure was made for those rubber compoundscontaining DTDM. In this case, the samples with DTDM were mixed for 3minutes after addition of the Flexzone 7P, after which, the mixingprocedure described for Examples 161-166 was followed.

The performance data in Table m show that carbon black productsaccording to the invention are useful in several different rubberformulations. In particular, carbon black products described in Examples4 and 5 reduce 70° C. Tan δ when using natural rubber, SBR-1500,orDuradene 715 in the fonnulation. Furthermore, addition of 0.8 phr ofDTDM to the rubber formulations containing carbon black products ofExamples 4 and 5 gives vulcanizates with higher hardness, modulus, andbound rubber, relative to the formulation without DTDM. It also resultsin lower elongation and 70° C. Tan δ and, in general, gives greatertensile strength and improved abrasion resistance.

Examples 181-188

These examples illustrate the use of the carbon black products ofExamples 120, 126, 139 and 140 and the comparative Example 160 inseveral different rubber formulations. The rubber compounds wereprepared by the method described for Examples 161-166 using formulationsselected Table I.

The performance data in Table IV show that carbon black productsaccording to the invention are useful in several different rubberformulations. Specifically, in a blend of NS-116 and NS-114,use ofcarbon black products from Examples 120, 126, 139and 140 gave increasedbound rubber and significant reductions in 70° C. Tan δ. In Duradene,carbon black products described in Examples 9 and 23 are especiallyuseful in reducing 70° C. Tan δ.

Examples 189-196

These examples illustrate the use of the carbon black products ofExamples 123, 127, 134 and 136 and the comparative Example 159 inseveral different rubber formulations. The rubber compounds wereprepared by the following method using formulations selected from TableI.

The polymer was milled in a Brabender mixer for 1 minute at 100° C. Amixture of ZnO and the carbon black product or comparative carbon blackwas added and mixed for 2 additional minutes. The stearic acid andFlexzone 7P antidegradent were added and mixed for 2 additional minutes.The sample was dumped and passed through an open mill 3 times. Thesample was allowed to cool and then transferred back into the Brabendermixer and mixed for 1 minute at 100° C. The curative package was thenadded, mixing continued for 1 minute, and the sample dumped then passedthrough a open mill 3 times.

Table V shows that these carbon black products are useful in severalrubber formulations including functionalized and unfunctionalizedsolution SBRs. Furthermore, use of carbon black product described inExample 123 in S-1216, Duradene 715,and NS-1 16 results in lower 70° C.Tan δ values as well as increased bound rubber. When compounded withNS-114,the carbon black product from Example 127 gave higher modulus,bound rubber and abrasion resistance, lower elongation and 70° C. Tan δ,and equal tensile strength and hardness.

Examples 197-200

These examples illustrate the use of the carbon black products ofExamples 129 and 135 and the comparative Example 160 in two differentrubber formulations. The rubber compounds were prepared by the themethod described in Examples 189-196 using formulations selected fromTable I.

Table VI shows that these carbon black products are useful in theserubber formulations using functionalized or unfunctionalized solutionSBRs. When using a blend of NS-116 and NS-114, increases in modulus,hardness, and bound rubber were observed. Sizable decreases in 70 ° C.Tan δ and elongation are also seen. In Duradene 715, modulus wasincreased while tensile strength, elongation at break, and 70° C. Tan δare all substantially reduced.

Examples 201-205

These examples illustrate the use of the carbon black products ofExample 155 and the comparative Example 160 in different rubberformulations. The rubber compounds were prepared by the the methoddescribed in Examples 189-196 using formulations selected from Table I.

Table VII shows that this carbon black product was useful in a number ofrubber formulations, specifically formulations that contained NR,emulsion SBR, or a functionalized solution SBRs selected from SL-574,RCTO-586, or TO-587.

Examples 206-215

These examples illustrate the use of the carbon black products ofExamples 154-158 and the comparative Example 159 in two rubberformulations. The rubber compounds were prepared by the the methoddescribed in Examples 189-196 using formulations selected from Table I.

As can be seen by inspection of the data in Table VIII below, a widerange of treatment levels as exemplified by the carbon black products inExamples 154-158 can have an impact on rubber performance properties.

These examples illustrate the use of the carbon black products ofExamples 137, 138, and 141 and the comparative Example 160 in two rubberformulations. The rubber compounds were prepared by the the methoddescribed in Examples 161-166 using formulations selected from Table I.

Table IX shows that these carbon black products were useful in severalrubber formulations including functionalized and unfunctionalizedsolution SBRs. In particular, the carbon black products in Examples 137,138, and 141 all showed lower 70° C. Tan δ values as well as increasedbound rubber in both rubber systems. In addition, the products inExample 137 and 138 also showed improvements in abrasion resistance.

Examples 222-235

These examples illustrate the use of the carbon black products ofExamples 142-147 and the comparative Example 160 in three rubberformulations. The rubber compounds were prepared by the the methoddescribed in Examples 161-166 using formulations selected from Table I.

Table X shows that these carbon black products were useful in the rubberformulations studied. In particular, all of the blacks studied showedreductions in 70° C. Tan δ values and increased bound rubber in bothfunctionalized and unfunctionalized solution SBRs with comparablehardness. Comparable hardness and 70° C. Tan δ values were found innatural rubber, with the carbon black product of Example 146 showing thegreatest reduction in Tan δ.

Examples 236-246

These examples illustrate the use of the carbon black products ofExamples 148-153 and the comparative Example 160 in two rubberformulations. The rubber compounds were prepared by the the methoddescribed in Examples 161-166 using formulations selected from Table I.

Table XI shows that these carbon black products were useful in rubberformulations. For example, when the carbon black products of Example148, 149, and 153 were compounded in Duradene 715 or a 70/30 blend ofNS-116 and NS-114, in general, abrasion resistance is either unchangedor improved while 70° C. Tan δ values were reduced.

Examples 247-262

These examples illustrate the use of the carbon black products ofExamples 119, 125, 128 and 130-133 and the comparative Example 160 invarious rubber formulations. The rubber compounds were prepared by thethe method described in Examples 161-166 using formulations selectedfrom Table I.

Table XII shows that these carbon black products were useful in rubberformulations. For example, when the carbon black product of Example 119was compounded with Duradene 715, SBR-1500, or a blend of NS-116 andNS-114, abrasion resistance was improved while 70° C. Tan δ values werereduced and the percentage of bound rubber increased. Use of carbonblack products from Examples 130-133 in Duradene 715 and Natural Rubbershowed that a wide range of carbon black treatment levels of this typecan have an impact on rubber performance properties.

Example 263

Preparation of a carbon black product

Ten grams of a carbon black with a surface area of 230 m2/g and a DBPAof 70 m2/g was added to a stirring solution of 3.06 g of3-amino-N-ethylpyridinium bromide in 72 g of water. Concentrated nitricacid (1.62 g) was added, and the mixture was stirred and heated to about70° C. A solution of 1.07 g NaNO₂ in about 5 g of water was added over afew minutes. The diazonium salt N₂ C₅ H₄ N(C₂ H₅)⁺⁺ was formed in situ,which reacted with the carbon black. After the reaction mixture wasstirred for one hour, the sample was dried in an oven at 125° C. Theproduct had a mean volume particle size of 0.18 microns. The product hadattached 3-C₅ H₄ N(C₂ H₅)⁺ groups.

Example 264

Preparation of a carbon black product

3-Amino-N-methylpyridinium iodide (3.92 g) was dissolved in 70 g ofwater. A solution of 2.58 g AgNO₃ in 6 g of water was added. Afterstirring for 15 minutes, the precipitate was removed by filtration and10 g of a carbon black with a surface area of 230 m2/g and a DBPA of 70m2/g was added. Concentrated nitric acid (1.62 g) was added, and themixture was stirred and heated to about 70° C. A solution of 1.07 gNaNO₂ in about 5 g of water was added over a few minutes. The diazoniumsalt N₂ C₅ H₄ CH₂ N(CH₃)⁺⁺ was formed in situ, which reacted with thecarbon black. Bubbles were released. After the reaction mixture wasstirred for about 40 minutes at 70° C. and then boiled for about 15minutes. The sample was dried in an oven at 125° C. The product had amean volume particle size of 0.23 microns. The product had a 325 meshresidue of 0.0% compared to 94% for the untreated carbon black. Theproduct had attached 3-C₅ H₄ N(CH₃)⁺ groups.

Example 265

Preparation of a carbon black product

Fifty grams of benzyltrimethylammonium chloride was added over 25minutes to cold 90% nitric acid. The mixture was kept below 10° C. forfive hours. Ice (500 g) was added, and the mixture was neutralized withKOH. The precipitate was removed by filtration. Ethanol (1 L) was addedand the mixture was filtered again. 3-Nitrobenzyltrimethylammoniumnitrate was recovered from the filtrate. This material was 75% pure byNMR. A mixture of 10 g of 3-Nitrobenzyltrimethylammonium nitrate, 14 gFe filings, 2 g of concentrated HCl and 400 g of water was boiled for2.5 hr. The mixture was neutralized with KOH and filtered to give anaqueous solution of 3-aminobenzyltrimethylammonium nitrate/chloride.

Fourteen grams of carbon black with a surface area of 230 m2/g and aDBPA of 70 m2/g was added to a stirring solution of 3.06 g of3-arninobenzyltrimethylammonium nitrate/chloride in 72 g of water.Concentrated nitric acid (1.62 g) was added, and the mixture was stirredand heated to about 70° C. A solution of 1.07 g NaNO₂ in about 5 g ofwater was added over a few minutes. The diazonium salt 3-N₂ C₆ H₄N(CH₃)⁺⁺ was formed in situ, which reacted with the carbon black. Afterthe reaction mixture was stirred for one hour, the sample was dried inan oven at 125° C. The product had a mean volume particle size of 0.18microns. The product had attached 3-N₂ C₆ H₄ CH₂ N(CH₃)₃ ⁺ groups.

Example 266

reparation of a carbon black product

Silver nitrite (30.9 g) was added to a solution of 41.4 g ofN-(4-aminophenyl)pyridinium chloride in 700 g of water and the mixturewas stirred at 70° C. for 11/2 hours. The mixture was filtered and 200 gof a carbon black with a surface area of 200 m2/g and a DBPA of 122mL/100 g was added. An additional one liter of water and 20 g ofconcentrated HCl were added. The diazonium salt N₂ C₆ H₄ NC₅ H₅ ++wasformed in situ, which reacted with the carbon black. Bubbles werereleased. The dispersion was stirred at 70°-80° C. for 21/2 hours andthen dried in an oven at 125° C. The product had attached C₆ H₄ NC₅ H₅ ⁺groups.

Example 267

Preparation of a carbon black product

In a modification of a procedure from U.S. Pat. No. 2,821,526, a mixtureof 250 g p-acetaminophenacyl chloride, 65 g of trimethylamine and about600 g of water was stirred for three days at room temperature. Anadditional 5 g of trimethylamine in 15 g water was added and the mixturewas heated at 60° C. for two hours. After cooling and filtering, 201 gconcentrated HCl was added and the solution was boiled for an hour.After cooling, 4 L of acetone was added and4-aminophenacyltrimethylammonium chloride hydrochloride was collected asa solid. 4-Aminophenacyltrimethylammonium chloride hydrochloride (10.1g) was suspended in 50 mL of ethanol. After addition of 4.1 gtriethylamine, the mixture was stirred for 40 minutes and heated atreflux for one hour. 4-Aminophenacyl-trimethylammonium chloride wascollected by filtration and washed with ethanol.4-Aminophenacyltrimethylammonium chloride (2.51 g) was dissolved inwater. Silver nitrite (1.69 g) was added, and the mixture was heated at70° C. for one hour. After filtering off the precipitate, 10 g of acarbon black with a surface area of 230 m2/g and a DBPA of 70 mL/100 gwas added. Water was added to bring the volume up to about 100 mL.Concentrated HCl (1.1 g) was added and the dispersion was heated withstirring at 70° C. for one hour. The diazonium salt N₂ C₆ H₄ COCH₂N(CH₃)₃ ⁺⁺ was formed in situ, which reacted with the carbon black.Bubbles were released. The product had attached C₆ H₄ COCH₂ N(CH₃)₃ ⁺groups.

Example 268

Preparation of a carbon black product

A solution of 2.12 g of 4-acetaminophenacyl chloride, 0.83 g of pyridineand 6.4 g of dimethylsulfoxide was stirred overnight. After addition ofan additional 0.8 g of pyridine and 1 g of dimethylsulfoxide, thesolution was stirred an additional 5 hours. Ether (50 mL) was added, andacetamidophenacylpyridinium chloride was collected by filtration. Theacetamidophenacylpyridinium chloride was dissolved in water, thesolution filtered and 1.7 g concentrated HCl was added. After boilingfor one hour, the solution was cooled, acetone was added, and4-aminophenacylpyridinium chloride hydrochloride was collected byfiltration. Two grams of 4-aminophenacylpyridinium chloridehydrochloride was dissolved in 15 g water and 4.5 g of a basic ionexchange resin (Amberlite IRA400-OH) was added. After stirring, theresin was removed by filtration and 4-aminophenacylpyridinium chloridewas collected as an aqueous solution.

A. solution of 1.3 g of 4-aminophenacylpyridinium chloride in 25 g ofwater was heated at reflux with 1 g silver nitrite for about 90 minutes.The precipitate was removed by filtration. Five grams of a carbon blackwith a surface area of 200 m2/g and a DBPA of 122 mL/100 g were addedand the mixture was heated to about 80° C. Concentrated HCl (0.52 g) wasadded and the dispersion was stirred an additional 11/2 hours. Thediazonium salt N₂ C₆ H₄ COCH₂ (NC₅ H₅)⁺⁺ was formed in situ, whichreacted with the carbon black. The product had attached C₆ H₄ COCH₂ (NC₅H₅)⁺ groups.

                                      TABLE I                                     __________________________________________________________________________    Rubber Formulations                                                           Formulation                                                                          A   B   C   D   E   F   G   H   I   J   K   L   M   N                  __________________________________________________________________________    NS-116 100     80  70                                                         NS-114     100 20  30                                                         Duradene 715           100 100                                                Natural Rubber                 100 100                                        SBR-1500                               100 100                                S-1216                                         100                            SL-574                                             100                        RCTO-586                                               100                    TO-587                                                     100                CB Product or                                                                        50  50  50  50  50  50  50  50  50  50  50  50  50  50                 Comparative                                                                   DTDM                       0.8     0.8     0.8                                ZnO    3   3   3   3   3   3   3   3   3   3   3   3   3   3                  Stearic Acid                                                                         2   2   2   2   2   2   2   2   2   2   2   2   2                      Flexzone 7P                                                                          1   1   1   1   1   1   1   1   1   1   i   1   1                      CBS    1.25                                                                              1.25                                                                              1.25                                                                              1.25                                                                              1.25                                                                              1.25                                                                              1.25                                                                              1.25                                                                              1.25                                                                              1.25                                                                              1.25                                                                              1.25                                                                              1.25                                                                              1.25               MBT    0.2 0.2 .                                                                             0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2                Sulfur 1.75                                                                              1.75                                                                              1.75                                                                              1.75                                                                              1.75                                                                              1.75                                                                              1.75                                                                              1.75                                                                              1.75                                                                              1.75                                                                              1.75                                                                              1.75                                                                              1.75                                                                              1.75               Total  159.2                                                                             159.2                                                                             159.2                                                                             159.2                                                                             159.2                                                                             160 159.2                                                                             160 159.2                                                                             160 159.2                                                                             159.2                                                                             159.2                                                                             159.2              __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________        Carbon       100% 300%                    Abrader                                                                            Abrader                        Black   Modulus                                                                            Modulus                                                                            Tensile Hardness                                                                           Bound                                                                             Tan δ                                                                      Tan δ                                                                       Index                                                                              Index                      Ex. Prod.                                                                             Form.                                                                             Mpa  Mpa  Mpa Elong.                                                                            Shore A                                                                            Rubber                                                                            0° C.                                                                     70° C.                                                                     14% Slip                                                                           21% Slip                   __________________________________________________________________________    161 118 D   4.41 21.38                                                                              21.54                                                                             305 74   44  0.640                                                                            0.126                                                                             124  153                        162 121 D   4.14 --   20.96                                                                             278 73   54.7                                                                              0.642                                                                            0.106                                                                             137  189                        163 122 D   4.18 20.01                                                                              20.72                                                                             309 74   44.3                                                                              0.634                                                                            0.117                                                                             108  139                        Comp.                                                                             160 D   3.69 --   14.34                                                                             257 71   35.7                                                                              0.613                                                                            0.160                                                                             100  100                        164 118 E   4.20 --   15.07                                                                             242 74   46.8                                                                              0.455                                                                            0.142                                                                              81  106                        165 121 E   5.66 --   15.62                                                                             214 77   53.8                                                                              0.439                                                                            0.135                                                                              75  107                        166 122 E   4.IO --   14.98                                                                             254 74   46.7                                                                              0.416                                                                            0.135                                                                              73  106                        Comp.                                                                             160 E   2.89 15.14                                                                              24.02                                                                             435 70   45.4                                                                              0.414                                                                            0.178                                                                             100  100                        __________________________________________________________________________

                                      TABLE III                                   __________________________________________________________________________        Carbon       100% 300%                    Abrader                                                                            Abrader                        Black   Modulus                                                                            Modulus                                                                            Tensile Hardness                                                                           Bound                                                                             Tan δ                                                                      Tan δ                                                                       Index                                                                              Index                      Ex. Prod.                                                                             Form.                                                                             Mpa  Mpa  Mpa Elong.                                                                            Shore A                                                                            Rubber                                                                            0° C.                                                                     70° C.                                                                     14% Slip                                                                           21% Slip                   __________________________________________________________________________    167 121 G   3.66 18.21                                                                              27.59                                                                             472 69   48.0                                                                              0.235                                                                            0.121                                                                             104  101                        168 121 H   3.87 19.32                                                                              28.16                                                                             436 71   51.9                                                                              0.210                                                                            0.102                                                                             100  115                        169 122 G   3.47 16.60                                                                              28.94                                                                             516 70   46.0                                                                              0.249                                                                            0.111                                                                              87   90                        170 123 H   3.16 15.57                                                                              28.30                                                                             518 70   42.6                                                                              0.241                                                                            0.146                                                                              91   90                        171 124 G   3.55 16.75                                                                              29.67                                                                             519 71   42.4                                                                              0.244                                                                            0.155                                                                             102   96                        Comp.                                                                             160 G   3.55 17.87                                                                              29.56                                                                             489 70   47.3                                                                              0.257                                                                            0.123                                                                             100  100                        172 121 I   3.42 18.82                                                                              25.11                                                                             386 72   40.7                                                                              0.297                                                                            0.159                                                                             107  116                        173 121 J   3.90 21.38                                                                              22.72                                                                             316 74   46.9                                                                              0.281                                                                            0.143                                                                             105  140                        174 122 I   3.09 15.4I                                                                              25.73                                                                             464 73   3i.2                                                                              0.294                                                                            0.173                                                                              91  114                        175 122 J   3.85 20.57                                                                              21.07                                                                             317 74   45.2                                                                              0.275                                                                            0.135                                                                              98  127                        176 124 I   3.98 18.60                                                                              22.40                                                                             354 73   35.7                                                                              0.279                                                                            0.172                                                                              90  103                        Comp.                                                                             160 I   2.91 15.76                                                                              25.36                                                                             438 70   34.7                                                                              0.322                                                                            0.180                                                                             100  100                        177 121 E   4.62 --   14.57                                                                             283 77   44.1                                                                              0.365                                                                            0.135                                                                              66  108                        178 121 F   4.11 --   16.15                                                                             241 74   49.8                                                                              0.458                                                                            0.130                                                                             104  130                        179 122 E   3.89 --   16.72                                                                             287 74   43.5                                                                              0.410                                                                            0.140                                                                              79  117                        180 122 F   4.26 --   16.91                                                                             257 75   46.3                                                                              0.406                                                                            0.127                                                                              94  139                        Comp.                                                                             160 E   3.17 16.88                                                                              20.52                                                                             350 72   39.6                                                                              0.421                                                                            0.161                                                                             100  100                        __________________________________________________________________________

                                      TABLE IV                                    __________________________________________________________________________        Carbon       100% 300%                    Abrader                                                                            Abrader                        Black   Modulus                                                                            Modulus                                                                            Tensile Hardness                                                                           Bound                                                                             Tan δ                                                                      Tan δ                                                                       Index                                                                              Index                      Ex. Prod.                                                                             Form.                                                                             Mpa  Mpa  Mpa Elong.                                                                            Shore A                                                                            Rubber                                                                            0° C.                                                                     70° C.                                                                     14% Slip                                                                           21% Slip                   __________________________________________________________________________    181 120 D   3.68 --   16.32                                                                             278 73   45.3                                                                              0.640                                                                            0.135                                                                             80    93                        182 126 D   3.16 16.20                                                                              19.55                                                                             349 73   55.8                                                                              0.630                                                                            0.122                                                                             87    94                        183 139 D   3.56 15.87                                                                              18.09                                                                             334 74   47.1                                                                              0.648                                                                            0.124                                                                             98   81                         184 140 D   3.02 15.13                                                                              19.97                                                                             373 72   46.3                                                                              0.662                                                                            0.135                                                                             103   95                        Comp.                                                                             160 D   3.60 16.88                                                                              20.58                                                                             354 75   39.9                                                                              0.622                                                                            0.166                                                                             100  100                        185 120 E   3.03 14.74                                                                              16.92                                                                             334 74   45.7                                                                              0.459                                                                            0.162                                                                             99    94                        186 126 E   3.87 --   12.84                                                                             238 75   49.9                                                                              0.460                                                                            0.146                                                                             84   120                        187 139 E   3.30 --   14.76                                                                             296 75   46.4                                                                              0.396                                                                            0.137                                                                             63   100                        188 140 E   2.41 11.60                                                                              18.34                                                                             428 72   45.5                                                                              0.409                                                                            0.170                                                                             70   101                        Comp.                                                                             160 E   3.15 --   15.06                                                                             283 73   44.1                                                                              0.468                                                                            0.163                                                                             100  100                        __________________________________________________________________________

                                      TABLE V                                     __________________________________________________________________________        Carbon       100% 300%                    Abrader                                                                            Abrader                        Black   Modulus                                                                            Modulus                                                                            Tensile Hardness                                                                           Bound                                                                             Tan δ                                                                      Tan δ                                                                       Index                                                                              Index                      Ex. Prod.                                                                             Form.                                                                             Mpa  Mpa  Mpa Elong.                                                                            Shore A                                                                            Rubber                                                                            0° C.                                                                     70° C.                                                                     14% Slip                                                                           21% Slip                   __________________________________________________________________________    189 123 K   4.85 18.31                                                                              18.56                                                                             312 65   30.2                                                                              0.373                                                                            0.168                                                                              85   99                        190 134 K   3.87 15.50                                                                              20.65                                                                             383 64   25.8                                                                              0.395                                                                            0.177                                                                              89   66                        Comp.                                                                             159 K   4.01 17.03                                                                              19.64                                                                             336 62   27.3                                                                              0.450                                                                            0.176                                                                             100  100                        191 123 E   4.25 --   5.07                                                                              260 62   32.3                                                                              0.375                                                                            0.175                                                                              88  110                        192 134 E   4.61 18.50                                                                              21.80                                                                             349 60   29.4                                                                              0.401                                                                            0.198                                                                              90   91                        Comp.                                                                             159 E   4.96 19.73                                                                              20.66                                                                             315 59   30.7                                                                              0.430                                                                            0.194                                                                             100  100                        193 123 B   3.62 --   23.33                                                                             386 69   30.86                                                                             0.278                                                                            0.141                                                                              92  104                        Comp.                                                                             159 B   3.42 --   23.41                                                                             402 69   28.36                                                                             0.297                                                                            0.146                                                                             100  100                        194 127 B   4.04 --   18.52                                                                             294 60   35  0.289                                                                            0.137                                                                             110  113                        Comp.                                                                             159 B   3.25 14.09                                                                              18.36                                                                             385 60   28.1                                                                              0.327                                                                            0.173                                                                             100  100                        195 136 B   3.61 --   20.94                                                                             447 62   27.7                                                                              -- 0.165                                                                              59   79                        Comp.                                                                             159 B   3.53 --   22.08                                                                             387 63   24.2                                                                              -- 0.157                                                                             100  100                        196 136 E   5.10 --   15.57                                                                             284 63   26.3                                                                              -- 0.171                                                                              41   74                        Comp.                                                                             159 E   4.54 --   20.56                                                                             316 63   21.4                                                                              -- 0.179                                                                             100  100                        __________________________________________________________________________

                                      TABLE VI                                    __________________________________________________________________________        Carbon       100% 300%                    Abrader                                                                            Abrader                        Black   Modulus                                                                            Modulus                                                                            Tensile Hardness                                                                           Bound                                                                             Tan δ                                                                      Tan δ                                                                       Index                                                                              Index                      Ex. Prod.                                                                             Form.                                                                             Mpa  Mpa  Mpa Elong.                                                                            Shore A                                                                            Rubber                                                                            0° C.                                                                     70° C.                                                                     14% Slip                                                                           21% Slip                   __________________________________________________________________________    197 129 C   3.29 14.57                                                                              19.99                                                                             389 75   37.7                                                                              0.665                                                                            0.142                                                                             90   116                        198 135 C   3.01 13.66                                                                              18.03                                                                             372 75   43.2                                                                              0.648                                                                            0.141                                                                             89   106                        Comp.                                                                             160 C   2.85 12.78                                                                              19.13                                                                             408 74   32.8                                                                              0.668                                                                            0.173                                                                             100  100                        199 129 E   3.24 --   12.90                                                                             272 77   36.1                                                                              0.405                                                                            0.162                                                                             80   117                        200 135 E   4.36 --   11.08                                                                             239 79   31.0                                                                              0.379                                                                            0.165                                                                             49    81                        Comp.                                                                             160 E   2.80 13.65                                                                              22.23                                                                             447 75   33.9                                                                              0.448                                                                            0.178                                                                             100  100                        __________________________________________________________________________

                                      TABLE VII                                   __________________________________________________________________________        Carbon       100% 300%                    Abrader                                                                            Abrader                        Black   Modulus                                                                            Modulus                                                                            Tensile Hardness                                                                           Bound                                                                             Tan δ                                                                      Tan δ                                                                       Index                                                                              Index                      Ex. Prod.                                                                             Form.                                                                             Mpa  Mpa  Mpa Elong.                                                                            Shore A                                                                            Rubber                                                                            0° C.                                                                     70° C.                                                                     14% Slip                                                                           21% Slip                   __________________________________________________________________________    201 155 I   3.56 14.91                                                                              23.63                                                                             468 74   33.8                                                                              0.291                                                                            0.192                                                                              83   85                        Comp.                                                                             160 I   3.40 15.57                                                                              26.95                                                                             492 74   34.2                                                                              0.327                                                                            0.201                                                                             100  100                        202 155 G   2.77 14.19                                                                              30.13                                                                             567 72   34.1                                                                              0.239                                                                            0.129                                                                              87   84                        Comp.                                                                             160 G   3.76 17.91                                                                              31.15                                                                             504 72   43.2                                                                              0.241                                                                            0.117                                                                             100  100                        203 155 L   3.77 13.36                                                                              19.14                                                                             325 75   39.1                                                                              0.273                                                                            0.124                                                                              92  114                        Comp.                                                                             160 L   2.96 13.39                                                                              21.22                                                                             430 73   37.3                                                                              0.300                                                                            0.149                                                                             100  100                        204 155 M   3.23 10.31                                                                              14.09                                                                             420 74   17.9                                                                              0.790                                                                            0.179                                                                              68   73                        Comp.                                                                             155 M   2.61  9.50                                                                              17.64                                                                             525 71   17.5                                                                              0.819                                                                            0.246                                                                             100  100                        205 155 N   3.22 13.19                                                                              23.12                                                                             536 78   33  0.332                                                                            0.185                                                                             104  103                        Comp.                                                                             160 N   3.83 15.06                                                                              19.54                                                                             408 80   27.1                                                                              0.354                                                                            0.225                                                                             100  100                        __________________________________________________________________________

                                      TABLE VIII                                  __________________________________________________________________________        Carbon       100% 300%                    Abrader                                                                            Abrader                        Black   Modulus                                                                            Modulus                                                                            Tensile Hardness                                                                           Bound                                                                             Tan δ                                                                      Tan δ                                                                       Index                                                                              Index                      Ex. Prod.                                                                             Form.                                                                             Mpa  Mpa  Mpa Elong.                                                                            Shore A                                                                            Rubber                                                                            0° C.                                                                     70° C.                                                                     14% Slip                                                                           21% Slip                   __________________________________________________________________________    206 154 A   4.08 17.75                                                                              22.13                                                                             362 63   37.5                                                                              0.792                                                                            0.173                                                                             101  134                        207 155 A   3.95 16.96                                                                              22.13                                                                             376 63   37.5                                                                              0.814                                                                            0.178                                                                             95   150                        208 156 A   3.14 15.15                                                                              15.66                                                                             300 62   41.1                                                                              0.785                                                                            0.149                                                                             86   152                        209 157 A   4.02 --   14.59                                                                             290 62   37.2                                                                              0.776                                                                            0.150                                                                             72   141                        210 158 A   3.46 --   16.42                                                                             357 61   32.8                                                                              0.783                                                                            0.180                                                                             84   130                        Comp.                                                                             159 A   3.76 15.25                                                                              19.94                                                                             375 67   24.6                                                                              0.777                                                                            0.233                                                                             100  100                        211 154 E   6.08 --   14.39                                                                             212 63   30.7                                                                              0.377                                                                            0.160                                                                             71   128                        212 155 E   6.78 --   12.30                                                                             178 66   24.9                                                                              0.325                                                                            0.148                                                                             51    91                        213 156 E   6.28 --   11.10                                                                             175 66   25.2                                                                              0.322                                                                            0.156                                                                             54   100                        214 157 E   5.90 --   10.62                                                                             187 68   23.4                                                                              0.309                                                                            0.166                                                                             47    83                        215 158 E   5.95 --   11.06                                                                             190 66   27.0                                                                              0.315                                                                            0.168                                                                             53    91                        Comp.                                                                             159 E   4.96 19.73                                                                              20.66                                                                             315 59   30.7                                                                              0.430                                                                            0.194                                                                             100  100                        __________________________________________________________________________

                                      TABLE IX                                    __________________________________________________________________________        Carbon       100% 300%                    Abrader                                                                            Abrader                        Black   Modulus                                                                            Modulus                                                                            Tensile Hardness                                                                           Bound                                                                             Tan δ                                                                      Tan δ                                                                       Index                                                                              Index                      Ex. Prod.                                                                             Form.                                                                             Mpa  Mpa  Mpa Elong.                                                                            Shore A                                                                            Rubber                                                                            0° C.                                                                     70° C.                                                                     14% Slip                                                                           21% Slip                   __________________________________________________________________________    216 137 D   4.21 22.24                                                                              23.04                                                                             310 73   44.3                                                                              0.591                                                                            0.127                                                                              94  111                        217 138 D   4.11 21.64                                                                              26.69                                                                             323 74   44.0                                                                              0.670                                                                            0.123                                                                              99  111                        Comp.                                                                             160 D   4.14 --   17.62                                                                             268 74   37.5                                                                              0.615                                                                            0.141                                                                             100  100                        218 141 D   3.98 18.90                                                                              19.23                                                                             305 73   44.9                                                                              0.611                                                                            0.118                                                                              94   80                        Comp.                                                                             160 D   4.05 19.56                                                                              22.38                                                                             337 72   38.3                                                                              0.586                                                                            0.142                                                                             100  100                        219 137 E   3.81 --   16.55                                                                             251 73   46.3                                                                              0.450                                                                            0.135                                                                             127  141                        220 138 E   4.00 --   16.16                                                                             241 74   46.1                                                                              0.440                                                                            0.138                                                                             114  131                        Comp.                                                                             160 E   3.74 --   17.56                                                                             272 73   39.7                                                                              0.312                                                                            0.157                                                                             100  160                        221 141 E   4.06 --   13.38                                                                             260 75   43.5                                                                              0.378                                                                            0.158                                                                              61   75                        Comp.                                                                             160 E   3.30 17.38                                                                              20.65                                                                             344 71   42.5                                                                              0.481                                                                            0.163                                                                             100  100                        __________________________________________________________________________

                                      TABLE X                                     __________________________________________________________________________        Carbon  100% 300%                         Abrader                                                                            Abrader                        Black   Modulus                                                                            Modulus                                                                            Tensile Hardness                                                                           Bound                                                                             Tan δ                                                                      Tan δ                                                                       Index                                                                              Index                      Ex. Prod.                                                                             Form.                                                                             Mpa  Mpa  Mpa Elong.                                                                            Shore A                                                                            Rubber                                                                            0° C.                                                                     70° C.                                                                     14% Slip                                                                           21% Slip                   __________________________________________________________________________    222 142 E   3.82 18.49                                                                              19.75                                                                             319 73   42.7                                                                              0.488                                                                            0.152                                                                             76   101                        223 143 E   3.49 16.70                                                                              18.96                                                                             332 73   42.2                                                                              0.466                                                                            0.164                                                                             77   108                        224 144 E   3.57 17.49                                                                              18.68                                                                             316 73   42.4                                                                              0.477                                                                            0.150                                                                             66   120                        225 145 E   3.35 17.23                                                                              18.56                                                                             328 73   41.6                                                                              0.531                                                                            0.160                                                                             64   97                         Comp.                                                                             160 E   3.21 16.19                                                                              21.51                                                                             377 72   41.2                                                                              0.494                                                                            0.169                                                                             100  100                        226 142 D   3.68 18.53                                                                              22.54                                                                             353 72   41.8                                                                              0.650                                                                            0.118                                                                             81   99                         227 143 D   3.62 17.85                                                                              22.62                                                                             366 72   43.1                                                                              0.664                                                                            0.134                                                                             89   108                        228 144 D   3.68 --   13.36                                                                             239 72   44.4                                                                              0.655                                                                            0.125                                                                             96   105                        229 145 D   3.92 --   15.80                                                                             259 72   42.9                                                                              0.678                                                                            0.126                                                                             81   99                         230 146 D   3.72 18.91                                                                              22.08                                                                             340 72   43.7                                                                              0.860                                                                            0.128                                                                             84   104                        231 147 D   3.87 --   17.90                                                                             285 72   45.1                                                                              0.643                                                                            0.119                                                                             84   109                        Comp.                                                                             160 D   3.73 17.51                                                                              20.16                                                                             336 73   40.0                                                                              0.682                                                                            0.155                                                                             100  100                        232 142 G   3.47 16.49                                                                              27.76                                                                             489 70   43.3                                                                              0.281                                                                            0.148                                                                             74   86                         233 145 G   3.44 16.45                                                                              27.80                                                                             495 70   43.8                                                                              0.251                                                                            0.145                                                                             74   46                         234 146 G   3.44 16.57                                                                              27.53                                                                             488 70   44.0                                                                              0.248                                                                            0.139                                                                             72   85                         235 147 G   3.89 17.81                                                                              28.28                                                                             478 71   44.4                                                                              0.267                                                                            0.156                                                                             76   92                         Comp.                                                                             160 G   3.88 18.40                                                                              28.78                                                                             470 71   49.1                                                                              0.262                                                                            0.146                                                                             100  100                        __________________________________________________________________________

                                      TABLE XI                                    __________________________________________________________________________        Carbon       100% 300%                    Abrader                                                                            Abrader                        Black   Modulus                                                                            Modulus                                                                            Tensile Hardness                                                                           Bound                                                                             Tan δ                                                                      Tan δ                                                                       Index                                                                              Index                      Ex. Prod.                                                                             Form.                                                                             Mpa  Mpa  Mpa Elong.                                                                            Shore A                                                                            Rubber                                                                            0° C.                                                                     70° C.                                                                     14% Slip                                                                           21% Slip                   __________________________________________________________________________    236 148 D   3.65 18.36                                                                              21.30                                                                             339 73   43.6                                                                              0.603                                                                            0.122                                                                             120  101                        237 149 D   3.60 --   17.24                                                                             287 73   43.7                                                                              0.635                                                                            0.124                                                                             120  114                        238 150 D   3.67 --   15.47                                                                             280 73   36.7                                                                              0.647                                                                            0.120                                                                              85   76                        239 151 D   3.74 1765 20.99                                                                             348 73   38.9                                                                              0.618                                                                            0.149                                                                             133  115                        240 152 D   3.36 16.50                                                                              20.77                                                                             358 73   40.1                                                                              0.651                                                                            0.148                                                                             117   94                        241 153 D   3.83 --   16.08                                                                             263 73   51.0                                                                              0.589                                                                            0.111                                                                             104  108                        Comp.                                                                             160 D   3.76 18.94                                                                              20.39                                                                             318 73   38.4                                                                              0.624                                                                            0.138                                                                             100  100                        242 148 E   3.52 15.21                                                                              15.87                                                                             266 73   49.3                                                                              0.430                                                                            0.136                                                                              93  134                        243 149 E   3.18 --   15.40                                                                             280 73   46.5                                                                              0.431                                                                            0.145                                                                             104  113                        244 150 E   3.48 --   15.57                                                                             292 73   38.4                                                                              0.412                                                                            0.140                                                                              68   95                        245 151 E   2.81 14.35                                                                              19.54                                                                             382 71   43.5                                                                              0.446                                                                            0.172                                                                              95  112                        246 153 E   4.96 --   10.63                                                                             173 78   39.8                                                                              0.406                                                                            0.136                                                                              53  100                        Comp.                                                                             160 E   2.79 --   12.87                                                                             261 70   45.6                                                                              0.462                                                                            0.164                                                                             100  100                        __________________________________________________________________________

                                      TABLE XII                                   __________________________________________________________________________        Carbon       100% 300%                                                        Black   Modulus                                                                            Modulus                                                                            Tensile Hardness                                                                           Bound                                                                             Tan δ                                                                      Tan δ                                                                       Abrader                                                                            Abrader                    Ex. Prod.                                                                             Form.                                                                             Mpa  Mpa  Mpa Elong.                                                                            Shore A                                                                            Rubber                                                                            0° C.                                                                     70° C.                                                                     Index                                                                              Index                      __________________________________________________________________________                                                  14% Slip                                                                           21% Slip                   247 119 E   3.63 --   14.43                                                                             246 74   46.1                                                                              0.439                                                                            0.142                                                                             107  126                        248 125 E   3.06 16.33                                                                              19.15                                                                             342 72   40.2                                                                              0.446                                                                            0.150                                                                             111  102                        249 130 E   4.38 --   14.69                                                                             247 76   42.0                                                                              0.439                                                                            0.134                                                                              75  105                        250 131 E   3.93 --   17.69                                                                             289 74   43.2                                                                              0.389                                                                            0.136                                                                              88  107                        251 132 E   4.17 --   16.88                                                                             266 74   47.4                                                                              0.460                                                                            0.136                                                                             101  177                        252 133 E   3.52 --   19.18                                                                             318 73   43.3                                                                              0.475                                                                            0.142                                                                             103  105                        Comp.                                                                             160 E   3.26 17.08                                                                              22.91                                                                             383 71   38.6                                                                              0.439                                                                            0.164                                                                              100 100                        253 119 D   3.70 --   19.08                                                                             299 73   45.6                                                                              0.691                                                                            0.127                                                                             109  133                        254 128 D   3.88 18.01                                                                              20.4                                                                              333 74   39.4                                                                              0.462                                                                            0.129                                                                             77   110                        Comp.                                                                             160 D   3.41 17.06                                                                              20.35                                                                             344 73   37.6                                                                              0.622                                                                            0.152                                                                             100  100                        255 119 I   3.38 18.8 22.68                                                                             350 72   41.1                                                                              0.272                                                                            0.151                                                                             113  114                        256 130 I   3.55 16.93                                                                              23.73                                                                             396 71   37.2                                                                              0.293                                                                            0.169                                                                             104  111                        Comp.                                                                             160 I   3.09 16.08                                                                              23.46                                                                             407 71   34.7                                                                              0.327                                                                            0.179                                                                             100  100                                                                      7% Slip                                                                            14% Slip                   257 119 G   3.56 17.13                                                                              29.20                                                                             505 71   37.9                                                                              0.256                                                                            0.132                                                                              96  105                        258 125 G   3.21 15.94                                                                              28.87                                                                             529 69   37.9                                                                              0.249                                                                            0.139                                                                              92   92                        259 130 G   3.27 16.55                                                                              27.70                                                                             505 69   41.5                                                                              0.233                                                                            0.115                                                                              97  106                        260 131 G   3.20 16.58                                                                              29.30                                                                             509 69   42.0                                                                              0.236                                                                            0.123                                                                             103  110                        261 132 G   3.32 16.65                                                                              26.82                                                                             485 70   43.6                                                                              0.250                                                                            0.153                                                                             103  108                        262 133 G   3.19 16.36                                                                              28.72.                                                                            508 69   42.4                                                                              0.251                                                                            0.128                                                                              93   93                        Comp.                                                                             160 G   3.57 18.29                                                                              28.09                                                                             472 70   41.7                                                                              0.252                                                                            0.127                                                                             100  100                        __________________________________________________________________________

Example 269

Preparation of a carbon black product

A cold solution of 3.56 g NaNO₂ in water was added to a solution of 10.2g 4,4'-methylenedianiline, 140 g of water and 19.7 g of concentrated HClthat was stirring in an ice bath. After stirring for about 15 minutes,the resulting solution of the diazonium salt was added to a suspensionof 200 g of a carbon black in 1.6 L of water that was stirring at roomtemperature. The carbon black had a surface area of 55 m2/g and DBPA of46 mL/100 g. After s g for 11/2 hours, the mixture was neutralized withNaOH and filtered. The carbon black product was washed with water anddried in an oven at 125° C. The carbon black product contained 0.332%nitrogen after Soxhlet extraction overnight with THF, compared to 0.081%nitrogen for the untreated carbon black. Therefore, the carbon blackproduct had 0.18 mmol/g of attached C₆ H₄ CH₂ C₆ H₄ NH₂ groups.

The claimed invention is:
 1. A process for preparing a carbon blackproduct having an organic group attached to the carbon black comprisingthe step of:reacting at least one diazonium salt with a carbon black inthe absence of an externally applied electric current sufficient toreduce the diazonium salt.
 2. A process of claim 1 wherein the reactingstep is carried out in an aprotic medium.
 3. A process of claim 1wherein the reacting step is carried out in a protic medium.
 4. Aprocess of claim 1 wherein the diazonium salt is generated in situ.
 5. Aprocess for preparing a carbon black product having an organic groupattached to the carbon black comprising the step of:reacting at leastone diazonium salt with a carbon black in a protic reaction medium.
 6. Aprocess of claim 5 wherein the diazonium salt is generated in situ froma primary amine.
 7. A process of claim 6 wherein the diazonium salt isgenerated in situ by reacting the primary amine, at least one nitriteand at least one acid.
 8. A process of claim 7 wherein the nitrite is ametal nitrite, and the acid and amine are present in a one to one molarratio.
 9. A process of claim 6 wherein the diazonium salt is generatedin situ by reacting the primary amine with a nitrite and the primaryamine contains a strong acid group.
 10. A process of claim 9 wherein theprimary amine is para-aminobenzenesulfonic acid (sulfanilic acid).
 11. Aprocess of claim 6 wherein the diazonium salt is generated in situ byreacting the primary amine with an aqueous solution of nitrogen dioxide.12. A process of claim 6 wherein the protic medium is an aqueous medium,and the primary amine is an amine of the formula A_(y) ArNH₂, inwhich:Ar is an aromatic or heteroaromatic radical; A, which can be thesame or different when y is greater than 1, is independently asubstituent on the aromatic radical selected from:a functional groupselected from the group consisting of R, OR, COR, COOR, OCOR, acarboxylate salt, halogen, CN, NR₂, SO₃ H, a sulfonate salt, OSO₃ H,OSO₃ -- salts, NR(COR), CONR₂, NO₂, OPO₃ H₂, a monobasic or dibasicphosphate salt, PO₃ H₂, a monobasic or dibasic phosphonate salt, N═NR,N₂ ⁺ X⁻, NR₃ ⁺ X⁻, PR₃ ⁺ X⁻, S_(k) R, SO₂ NRR', SO₂ SR, SNRR', SSO₃ H, aSSO₃ ⁻ salt, SNQ, SO₂ NQ, CO₂ NQ, S-(1,4-piperazinediyl)-SR,2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR, and SO₂ R; and a linear,branched or cyclic hydrocarbon radical, unsubstituted or substitutedwith one or more of said functional groups; where R and R', which can bethe same or different, are hydrogen; branched or unbranched C₁ -C₂₀unsubstituted or substituted alkyl, alkenyl, or alkynyl; unsubstitutedor substituted aryl; unsubstituted or substituted heteroaryl;unsubstituted or substituted alkylaryl; or unsubstituted or substitutedarylalkyl; whereink is an integer from 1 to 8; X- is a halide or ananion derived from a mineral or organic acid; y is an integer from 1 tothe total number of --CH radicals present in the aromatic radical; and Qis (CH₂)_(w), (CH₂)_(x) O(CH₂)_(z), (CH₂)_(x) NR(CH₂)_(z), or (CH₂)_(x)S(CH₂)_(z), where x is 1 to 6, z is 1 to 6, and w is 2 to
 6. 13. Aprocess of claim 12 wherein:Ar is an aromatic radical selected from thegroup consisting of phenyl, naphthyl, anthryl, phenanthryl, biphenyl,and pyridyl; A, which can be the same or different when y is greaterthan 1, is independently a substituent on the aromatic radical selectedfrom:a functional group selected from the group consisting of R, OR,COR, COOR, OCOR, COOLi, COONa, COOK, COO⁻ NR₄ ⁺, halogen, CN, NR₂, SO₃H, SO₃ Li, SO₃ Na, SO₃ K, SO₃ ⁻ NR₄ ⁺, NR(COR), CONR₂, NO₂, PO₃ H₂, PO₃HNa, PO₃ Na₂,N═NR, N₂ ⁺ X⁻, NR₃ ⁺ X⁻, PR₃ ⁺ X⁻, S_(k) R, SOR, and SO₂ R;and a linear, branched or cyclic hydrocarbon radical, unsubstituted orsubstituted with one or more of said functional groups; where R ishydrogen; branched or unbranched C₁ -C₂₀ unsubstituted or substitutedalkyl, alkenyl or alkynyl; unsubstituted or substituted aryl;unsubstituted or substituted heteroaryl; unsubstituted or substitutedalkylaryl; or unsubstituted or substituted arylalkyl; wherein k is aninteger from 1 to 8; X- is a halide or an anion derived from a mineralor organic acid; and y is an integer from 1 to 5 when Ar is phenyl, 1 to7 when Ar is naphthyl, 1 to 9 when Ar is anthryl, phenanthryl, orbiphenyl, and 1 to 4 when Ar is pyridyl.
 14. A process of claim 12,wherein:Ar is an aromatic radical selected from the group consisting ofphenyl, benzothiazolyl, and benzothiadiazolyl; A, which can be the sameor different when y is greater than 1, is independently a substituent onthe aromatic radical selected from:a functional group selected from thegroup consisting of S_(k) R, SSO₃ H, SO₂ NRR', SO₂ SR, SNRR', SNQ, SO₂NQ, CO₂ NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), and2-(1,3-dithiolanyl); and a linear, branched or cyclic hydrocarbonradical, unsubstituted or substituted with one or more of saidfunctional groups; where R and R', which can be the same or different,are hydrogen; branched or unbranched C₁ -C₂₀ unsubstituted orsubstituted alkyl, alkenyl, or alkynyl; unsubstituted or substitutedaryl; unsubstituted or substituted heteroaryl; unsubstituted orsubstituted alkylaryl; or unsubstituted or substituted arylalkyl;y is aninteger from 1-5 when Ar is phenyl, 1-4 when Ar is benzothiazolyl, and1-3 when Ar is benzothiadiazolyl; k is an integer from 1 to 8; and Q is(CH₂)_(w), (CH₂)_(x) O(CH₂)_(z), (CH₂)_(x) NR(CH₂)_(z), or (CH₂)_(x)S(CH₂)_(z), where x is 1 to 6, z is 1 to 6, and w is 2 to
 6. 15. Aprocess of claim 12, wherein R and R' are selected from NH₂ --C₆ H₄, CH₂CH₂ --C₆ H₄ --NH₂, CH₂ --C₆ H₄ --NH₂, and C₆ H₅.
 16. A process of claim12, wherein A is (CH₂)_(q) S_(k) (CH₂)_(r) Ar, where k is an integerfrom 1 to 8, q is an integer from 0 to 4, r is an integer from 0-4, andAr is a substituted or unsubstituted aryl or heteroaryl group.
 17. Aprocess of claim 6 wherein the primary amine is an aminobenzenesulfonicacid or a salt thereof, an aminobenzenecarboxylic acid or a saltthereof, or bis-para-H₂ N--(C₆ H₄)--S_(k) --(C₆ H₄)--NH₂ wherein k is aninteger from 2 to
 8. 18. A process of claim 17 wherein the primary amineis para-aminobenzenesulfonic acid (sulfanilic acid).
 19. A process ofclaim 17, wherein the primary amine is bis-para-H₂ N--(C₆ H₄)--S_(k)--(C₆ H₄)--NH₂ and k is 2, (para-aminophenyldisulfide).
 20. A process ofclaim 6 wherein the primary amine is H₂ NArS_(k) Ar', where k is aninteger from 2 to 4, Ar is phenylene, and Ar' is benzothiazolyl.
 21. Aprocess of claim 6 wherein the primary amine is H₂ NArS_(k) ArNH₂, wherek is an integer from 2 to 4 and Ar is benzothiazolylene.
 22. A processof claim 21 wherein k is
 2. 23. A process of claim 6 wherein the primaryamine is H₂ NArSH, where Ar is phenylene or benzothiazolylene.
 24. Aprocess of claim 5 wherein the diazonium salt is generated in situ. 25.A process of claim 5 wherein the diazonium salt is generated from aprimary amine separately from the reacting step.
 26. A process of claim25 wherein the protic medium is an aqueous medium, and the primary amineis an amine of the formula A_(y) ArNH₂, in which:Ar is an aromatic orheteroaromatic radical; A, which can be the same or different when y isgreater than 1, is independently a substituent on the aromatic radicalselected from:a functional group selected from the group consisting ofR, OR, COR, COOR, OCOR, a carboxylate salt, halogen, CN, NR₂, SO₃ H, asulfonate salt, OSO₃ H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂, OPO₃ H₂, amonobasic or dibasic phosphate salt, PO₃ H₂, a monobasic or dibasicphosphonate salt, N═NR, N₂ ⁺ X⁻, NR₃ ⁺ X⁻, PR₃ ⁺ X⁻, S_(k) R, SO₂ NRR',SO₂ SR, SNRR', SSO₃ H, a SSO₃ ⁻ salt, SNQ, SO₂ NQ, CO₂ NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR,and SO₂ R; and a linear, branched or cyclic hydrocarbon radical,unsubstituted or substituted with one or more of said functional groups;where R and R', which can be the same or different, are hydrogen;branched or unbranched C₁ -C₂₀ unsubstituted or substituted alkyl,alkenyl, or alkynyl; unsubstituted or substituted aryl; unsubstituted orsubstituted heteroaryl; unsubstituted or substituted alkylaryl; orunsubstituted or substituted arylalkyl; whereink is an integer from 1 to8; X- is a halide or an anion derived from a mineral or organic acid; yis an integer from 1 to the total number of --CH radicals present in thearomatic radical; and Q is (CH₂)_(w), (CH₂)_(x) O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or (CH₂)_(x) S(CH₂)_(z), where x is 1 to 6, z is 1 to 6,and w is 2 to
 6. 27. A process of claim 25 wherein:Ar is an aromaticradical selected from the group consisting of phenyl, naphthyl, anthryl,phenanthryl, biphenyl, and pyridyl; A, which can be the same ordifferent when y is greater than 1, is independently a substituent onthe aromatic radical selected from:a functional group selected from thegroup consisting of R, OR, COR, COOR, OCOR, COOLi, COONa, COOK, COO⁻ NR₄⁺, halogen, CN, NR₂, SO₃ H, SO₃ Li, SO₃ Na, SO₃ K, SO₃ ⁻ NR₄ ⁺, NR(COR),CONR₂, NO₂, PO₃ H₂, PO₃ HNa, PO₃ Na₂, N═NR, N₂ ⁺ X⁻, NR₃ ⁺ X⁻, PR₃ ⁺ X⁻,S_(k) R, SOR, and SO₂ R; and a linear, branched or cyclic hydrocarbonradical, unsubstituted or substituted with one or more of saidfunctional groups; where R is hydrogen; branched or unbranched C₁ -C₂₀unsubstituted or substituted alkyl, alkenyl, or alkynyl; unsubstitutedor substituted aryl; unsubstituted or substituted heteroaryl;unsubstituted or substituted alkylaryl; or unsubstituted or substitutedarylalkyl; whereink is an integer from 1 to 8; X- is a halide or ananion derived from a mineral or organic acid; and y is an integer from 1to 5 when Ar is phenyl, 1 to 7 when Ar is naphthyl, 1 to 9 when Ar isanthryl, phenanthryl, or biphenyl, and 1 to 4 when Ar is pyridyl.
 28. Aprocess of claim 25, wherein:Ar is an aromatic radical selected from thegroup consisting of phenyl, benzothiazolyl, and benzothiadiazolyl; A,which can be the same or different when y is greater than 1, isindependently a substituent on the aromatic radical selected from:afunctional group selected from the group consisting of S_(k) R, SSO₃ H,SO₂ NRR', SO₂ SR, SNRR', SNQ, SO₂ NQ, CO₂ NQ, S-(1,4-piperazinediyl)-SR,2-(1,3-dithianyl), and 2-(1,3-dithiolanyl); and a linear, branched orcyclic hydrocarbon radical, unsubstituted or substituted with one ormore of said functional groups; where R and R', which can be the same ordifferent, are hydrogen; branched or unbranched C₁ -C₂₀ unsubstituted orsubstituted alkyl, alkenyl, or alkynyl; unsubstituted or substitutedaryl; unsubstituted or substituted heteroaryl; unsubstituted orsubstituted alkylaryl; or unsubstituted or substituted arylalkyl; y isan integer from 1-5 when Ar is phenyl, 1-4 when Ar is benzothiazolyl,and 1-3 when Ar is benzothiadiazolyl; k is an integer from 1 to 8; and Qis (CH₂)_(w), (CH₂)_(x) O(CH₂)_(z), (CH₂)_(x) NR(CH₂)_(z), or (CH₂)_(x)S(CH₂)_(z), where x is 1 to 6, z is 1 to 6, and w is 2 to
 6. 29. Aprocess of claim 26, wherein R and R' are selected from NH₂ --C₆ H₄, CH₂CH₂ --C₆ H₄ --NH₂, CH₂ --C₆ H₄ --NH₂, and C₆ H₅.
 30. A process of claim26, wherein A is (CH₂)_(q) S_(k) (CH₂)_(r) Ar, where k is an integerfrom 1 to 8, q is an integer from 0 to 4, r is an integer from 0-4, andAr is a substituted or unsubstituted aryl or heteroaryl group.
 31. Aprocess of claim 25 wherein the primary amine is an aminobenzenesulfonicacid or a salt thereof, an aminobenzenecarboxylic acid or a saltthereof, or bis-para-H₂ N--(C₆ H₄)--S_(k) --(C₆ H₄)--NH₂ wherein k is aninteger from 2 to
 8. 32. A process of claim 31 wherein the primary amineis para-aminobenzenesulfonic acid (sulfanilic acid).
 33. A process ofclaim 31 wherein the primary amine is bis-para-H₂ N--(C₆ H₄)--S_(k)--(C₆ H₄)--NH₂ and k is 2, (para-aminophenyldisulfide).
 34. A process ofclaim 25 wherein the primary amine is H₂ NArS_(k) Ar', where k is aninteger from 2 to 4, Ar is phenylene, and Ar' in benzothiazolyl.
 35. Aprocess of claim 25 wherein the primary amine is H₂ NArS_(k) ArNH₂,where k is an integer from 2 to 4 and Ar is benzothiazolylene.
 36. Aprocess of claim 25 wherein the primary amine is H₂ NArSH, where Ar isphenylene or benzothiazolylene.
 37. A process of claim 5 wherein theprotic reaction medium is an aqueous medium.
 38. A process of claim 37wherein the organic group of the diazonium salt is substituted orunsubstituted and is selected from the group consisting of an aliphaticgroup, a cyclic organic group, or an organic compound having analiphatic portion and a cyclic portion.
 39. A process of claim 5 whereinthe protic reaction medium is water.
 40. A process of claim 5 whereinthe protic medium is an alcohol-based medium.
 41. A process forproducing a carbon black product having an organic group attached to thecarbon black, comprising the steps ofintroducing a carbon black and atleast one diazonium salt into a pelletizer; and reacting said diazoniumsalt with said carbon black.
 42. The process of claim 41, wherein thediazonium salt is reacted with the carbon black in the presence ofwater.
 43. The process of claim 41, wherein the diazonium salt isintroduced as an aqueous solution or slurry.
 44. The process of claim41, wherein the carbon black product is pelletized.
 45. The process ofclaim 43, wherein the carbon black product is pelletized.
 46. A processfor producing a carbon black product having an organic group attached tothe carbon black, comprising the steps ofgenerating a diazonium salt inthe presence of carbon black in a pelletizer; and reacting saiddiazonium salt with said carbon black.
 47. The process of claim 46,wherein the diazonium salt is generated in the presence of water. 48.The process of claim 46, wherein the diazonium salt is generated from atleast one primary amine, at least one acid, and at least one nitrite.49. The process of claim 47, wherein the diazonium salt is generatedfrom at least one primary amine, at least one acid, and at least onenitrite.
 50. The process of claim 49, wherein the nitrite is introducedinto the pelletizer as an aqueous solution.
 51. The process of claim 49,wherein the amine is introduced into the pelletizer as an aqueoussolution or slurry of an acid salt of the amine.
 52. The process ofclaim 49, wherein the nitrite is introduced into the pelletizer as anaqueous solution and the amine is introduced into the pelletizer as anaqueous solution or slurry of an acid salt of the amine.
 53. The processof claim 49, wherein the amine and the carbon black are introduced intothe pelletizer as a dry mixture.